阅读说明：本技术 粘合剂组合物 (Adhesive composition ) 是由 L·赫尔伯特 N·斯威尼 B·迪根 A·D·梅萨纳 M·加利根 于 2018-04-17 设计创作，主要内容包括：本发明提供一种粘合剂组合物,该粘合剂组合物有时候是包括第一部分和第二部分的两部分构造,所述第一部分含有(甲基)丙烯酸酯组分、有机过氧化物和含乙缩醛的自由基可固化组分,并且所述第二部分含有(甲基)丙烯酸酯组分和苯甲酰基硫脲衍生物或苯甲酰基硫代氨基甲酸酯衍生物。(The present invention provides a kind of adhesive composition; the adhesive composition is sometimes two parts construction for including first part and second part; (methyl) acrylate component, organic peroxide and the free radical curable components containing acetal are contained in the first part, and the second part contains (methyl) acrylate component and benzoylthioureas derivative or benzoylthio carbamate derivatives.)

1. a kind of adhesive composition of two parts construction, described adhesive composition include:

(a) part (A), (A) partially include (methyl) acrylate component, organic peroxide and containing acetal from By base curable components；And

(b) part (B), (B) partially include (methyl) acrylate component and benzoylthioureas derivative or benzoyl Base thiocarbamate derivative.

2. adhesive composition according to claim 1, wherein the free radical curable components containing acetal by with The compound of lower general structure indicates:

Wherein R¹It is H, CH₃Or CN；

R²It is multivalence C₁To C₈Alkyl chain, C₆To C₁₂Aryl or C₃To C₈Naphthenic base；And

N is 1-4.

3. composition according to claim 1, wherein the free radical curable components containing acetal are by following general The compound of structure indicates:

Wherein R¹It is C₁-C₃₀Alkyl, C₆-C₃₀Aryl, ester or carbamate；And

R²It is divalent unsaturation C₂-C₄₀Linker (such as it can be derived from dicarboxylic acids, the dicarboxylic acids is selected from maleic acid, rich horse Acid, itaconic acid, glutaconate, traumatic acid, glutinicacid and mesaconic acid).

4. composition according to claim 1, wherein the free radical curable components containing acetal are by following general The compound of structure indicates:

Wherein R¹It is C₁-C₈Alkyl, C₆-C₁₂Aryl or C₃-C₈Naphthenic base；And

R²It is divalent unsaturation C₂-C₆₀Linker.

5. composition according to claim 4, wherein the R of the free radical curable components containing acetal²Derivative is free From tricarboxylic acids below: citric acid, isocitric acid, aconitic acid and trimesic acid.

6. composition according to claim 1, wherein the free radical curable components containing acetal are by selected from following The compound in group that formula is constituted indicates:

7. composition according to claim 1, wherein (A) part or (B) part at least one of it is described (methyl) acrylate component is selected from the group being made up of: (methyl) methyl acrylate, (methyl) acrylic acid, (methyl) propylene Acetoacetic ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid Isobutyl ester, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid Cyclohexyl, the positive heptyl ester of (methyl) acrylic acid, (methyl) n-octyl, (methyl) 2-EHA, (methyl) third Olefin(e) acid nonyl ester, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) phenyl acrylate, (methyl) propylene Sour toluene base ester, (methyl) benzyl acrylate, (methyl) acrylic acid 2- methoxy acrylate, (methyl) acrylic acid 3- methoxyl group fourth Ester, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) octadecyl acrylate, (first Base) glycidyl acrylate, (methyl) acrylic acid 2- amino ethyl ester, γ-(methyl) acryloxypropyl trimethoxy Silane, (methyl) acrylic acid-ethylene oxide adduct, (methyl) acrylic acid trifluoromethyl methyl esters, (methyl) acrylic acid 2- trifluoro Methylethyl, (methyl) acrylic acid 2- perfluoro-ethyl ethyl ester, (methyl) acrylic acid 2- perfluoro-ethyl -2- perfluoro butyl ethyl ester, (first Base) acrylic acid 2- perfluor ethyl ester, (methyl) perfluoroethyl methyl esters, (methyl) acrylic acid enjoys a double blessing methyl fluoride methyl esters, (methyl) third Olefin(e) acid 2- perfluoro-methyl -2- perfluoro-ethyl methyl esters, (methyl) acrylic acid 2- perfluoro hexyl ethyl ester, (methyl) acrylic acid 2- perfluor last of the ten Heavenly stems Base ethyl ester, (methyl) acrylic acid 2- perfluor cetyl ethyl ester, ethoxylated trimethylolpropane triacrylate, trihydroxy methyl Propane trimethyl acrylic ester, dipentaerythritol monohydroxypentaacryande, pentaerythritol triacrylate, three hydroxyl of ethoxylation Propane tri, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, pentaerythrite tetrapropylene acid Ester, 1,2- butanediol diacrylate, trimethylolpropane ethoxylate three (methyl) acrylate, glyceryl propoxylation Object three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol monohydroxy five (methyl) propylene Acid esters, three (propylene glycol) two (methyl) acrylate, neopentyl glycol propoxylate two (methyl) acrylate, 1,4- butanediol Two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, Ethoxylated bisphenol A bis- (methyl) acrylate and combinations thereof.

8. composition according to claim 1, wherein the benzoylthioureas derivative or benzoylthio amino Carbamate derivatives are indicated by the compound of following general structure:

Wherein Z is O or N-R, and wherein R is selected from hydrogen, alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl group, carbonyl, alkylidene (methyl) propylene Acid esters, carboxyl or sulfonic acid foundation or R ' are attached to the direct key of phenyl ring；R ' is selected from hydrogen, alkyl, alkenyl, naphthenic base, virtue Base, hydroxyalkyl, hydroxyalkenyl group, alkylene ether, alkenylene ether, carbonyl, alkylidene (methyl) acrylate, carboxyl, nitroso or Sulfonic acid foundation；X is halogen, alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl group, alkoxy, amino, carboxyl, nitroso, sulfonic group, hydroxyl Base or halogenated alkyl；And Y is-SO₂NH- ,-CONH- ,-NH- and-PO (NHCONHCSNH₂)NH-；And n is 0 or 1, and m It is 1 or 2；Or

Wherein R and R' is independently selected from hydrogen, alkyl, alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl group, alkylidene (methyl) acrylic acid Perhaps R and R' is collectively formed containing carbocyclic ring or is to be connected to benzene containing heteroatomic ring or R' for ester, carbonyl, carboxyl or sulfonic acid foundation The direct key of ring；X is halogen, alkyl, alkenyl, naphthenic base, hydroxyalkyl, hydroxyalkenyl group, alkoxy, amino, alkylene ether, sub- alkene Base ether, alkylidene (methyl) acrylate, carbonyl, carboxyl, nitroso, sulfonic group, hydroxyl or halogenated alkyl；And Y is- SO₂NH- ,-CONH- ,-NH- and-PO (NHCONHCSNH₂)NH-；And n is 0 or 1, and m is 1 or 2.

9. composition according to claim 1, wherein the benzoylthioureas derivative or benzoylthio amino Carbamate derivatives are indicated by the compound of following general structure:

Wherein R, X, Y and n are as defined above, and X ' is defined such as X.

10. composition according to claim 1, wherein the benzoylthioureas derivative or benzoylthio amino Carbamate derivatives are indicated by the compound of following general structure:

Wherein R, R ', X, Y and n it is as defined above, and m is 2.

11. adhesive composition according to claim 1, further includes block copolymer.

12. a kind of method for preparing two-part adhesive composition, which comprises

(a) part (A) is formed, (A) partially including (methyl) acrylate component, organic peroxide and contains acetal Free radical curable components；And

(b) part (B) is formed, (B) partially includes (methyl) acrylate component and benzoylthioureas derivative or benzene Formoxyl thiocarbamate derivative.

13. a kind of method that first surface is adhered to second surface, which comprises

Two parts composition is provided, two parts composition includes:

(a) part (A), (A) partially include (methyl) acrylate component, organic peroxide and containing acetal from By base curable components；And

(b) part (B), (B) partially include (methyl) acrylate component and benzoylthioureas derivative or benzoyl Base thiocarbamate derivative.

14. according to the method for claim 13, wherein when by described in (A) is partially partially mixed with (B) and is applied at least When on one substrate, the composition has at most 5 minutes open hour, and when the substrate matches clock synchronization, they have About 20 minutes or shorter curing time at 80 DEG C；And when with being less than fixation in 5 minutes under the bonding that will support 3Kg Between.

15. according to the method for claim 13, wherein will described in (A) partially and (B) partially with (A) partially with (B) The ratio that volume ratio between part is 1:10 to 10:1 mixes.

16. a kind of adhesive composition, comprising:

(a) (methyl) acrylate component；

(b) solidification packet, the solidification packet includes organic peroxide and benzoylthioureas derivative or benzoylthio ammonia Carbamate derivative；And

(c) the free radical curable components containing acetal.

17. composition according to claim 1 further comprises reactive acid constituents.

18. composition according to claim 17, wherein the reactivity acid constituents is (methyl) acrylic acid.

19. composition according to claim 17, wherein the reactivity acid constituents is sulfonic acid or sulfonic acid, phosphorus Acid, phosphoric acid derivatives and phosphate or acrylic acid.

Technical field

The present invention provides adhesive composition, described adhesive composition be sometimes include first part and second Two parts construction divided, the first part contain (methyl) acrylate component, organic peroxide and containing acetals (acetal) free radical curable components, and the second part contains (methyl) acrylate component and benzoyl sulphur Urea derivative or benzoylthio carbamate (benzoylthiourethane) derivative.

The brief description of the relevant technologies

Acrylic based binders composition is well-known.See, for example, U.S. Patent number 4,536,546 (Briggs). Although the adhesive based on this technology is by Illinois Worktools Inc. (Illinois Tool in Chicago, IL city Works Inc.) with the sale of trade name PLEXUS MA 300 and 310, but they may show unpleasant stink, and And it is toxic when operating, this is the significant drawback that it is used.

The first part and second part have sufficiently low viscosity, to be easy to be distributed with pumping equipment.In order to be formed This adhesive mixes the first part and second part, and the mixture has viscosity higher immediately upon mixing, So that after being applied on surface within the open hour of mixture, described adhesive will not sagging (sag), drippage (drip) or It migrates (migrate), and mixed first part and second part is allowed to solidify.Term " open hour " refers to adhesive Pass through the time between mixing and solidifying.

Recently, the researcher of Henkel (Henkel) invents and develops based on benzoylthioureas derivative or benzoyl The curing accelerator technology of base thiocarbamate derivative.For this purpose, U.S. Patent Application Publication No. US 2014/0004354 A kind of two-part curable compositions are provided, the composition includes:

Part A: one or more compounds in following structure I or IA:

Wherein Z is O or N-R, and wherein R is selected from hydrogen, alkyl, alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl group, alkylidene (methyl) Acrylate, carbonyl, carboxyl or sulfonic acid foundation (sulfonato), R' are selected from hydrogen, alkyl, alkenyl, aryl, hydroxyalkyl, hydroxyl alkene Base, alkylidene (methyl) acrylate, carbonyl, carboxyl or sulfonic acid foundation or R and R' are collectively formed containing carbocyclic ring or containing hetero atom Ring or R' be the direct key for being connected to phenyl ring；X is halogen, alkyl, alkenyl, naphthenic base, hydroxyalkyl, hydroxyalkenyl group, alcoxyl Base, amino, alkylene ether, alkenylene ether, alkylidene (methyl) acrylate, carbonyl, carboxyl, nitroso, sulfonic group (sulfonate), hydroxyl or halogenated alkyl；And Y is-SO₂NH- ,-CONH- ,-NH- and-PO (NHCONHCSNH₂)NH-；And And n is 0 or 1, and m is 1 or 2, or

Wherein R and R' is independently selected from hydrogen, alkyl, alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl group, alkylidene (methyl) propylene Perhaps R and R' is collectively formed containing carbocyclic ring or is to be connected to containing heteroatomic ring or R' for acid esters, carbonyl, carboxyl or sulfonic acid foundation The direct key of phenyl ring；X is halogen, alkyl, alkenyl, naphthenic base, hydroxyalkyl, hydroxyalkenyl group, alkoxy, amino, alkylene ether, Asia Alkene ether, alkylidene (methyl) acrylate, carbonyl, carboxyl, sulfonic group, hydroxyl or halogenated alkyl；And Y is-SO₂NH-、- CONH- ,-NH- and-PO (NHCONHCSNH₂)NH-；And n is 0 or 1, and m is 1 or 2；And

Part B: oxidant,

Wherein at least one of part A or part B include (methyl) acrylate component.

But existing composition do not have for quickly fixed needed for assembled layers casting die such as hand-held display device and Good adhesion property, and make the ability of the unsticking of the substrate cooperated therebetween with the composition adhesiveness.In the presence of to this The needs of composition.

There is a need for being able on the glass, composite material and engineering plastics of various substrates such as ink coating and/or between Firm connection is formed, while there is the adhesive composition of the ability of unsticking when needed.In this way, if final use Family needs to reuse, recycles or remove part, they can do so.Temperature for thermal activation unsticking, lower than 100 DEG C It is preferred, in order to avoid damage substrate.

Summary of the invention

The present invention provides the solutions for this demand and greater demand.

Sometimes the Invention adhesive compositions for two parts construction include first part (A) and second part (B), institute It states first part (A) and contains (methyl) acrylate component, organic peroxide and (methyl) acrylate group containing acetal Point, and the second part (B) contains (methyl) acrylate component and benzoylthioureas derivative or benzoyl sulphur For carbamate derivatives.

When the first part and second part are mixed and are applied on the substrate of at least one cooperation to be bonded, institute Composition is stated by at most 5 minutes open hour, and when substrate cooperation, their set time is in about room temperature It would be about under (23 DEG C) 5 minutes or less.

More specifically, providing a kind of two-part adhesive composition, comprising:

(a) first part, the first part contain (methyl) acrylate component, organic peroxide and contract containing second The free radical curable components of aldehyde；And

(b) second part, the second part contain (methyl) acrylate component and benzoylthioureas derivative or Benzoylthio carbamate derivatives.

In another aspect of the invention, a kind of method for preparing two-part adhesive composition, the method are provided Include:

(a) first part (A) is formed, the first part (A) contains (methyl) acrylate component, organic peroxide And the free radical curable components containing acetal；And

(b) second part (B) is formed, the second part (B) contains (methyl) acrylate component and benzoyl sulphur Urea derivative or benzoylthio carbamate derivatives.

In another aspect, provide a kind of method that first surface is adhered to second surface, the method includes with Lower step:

Two parts composition is provided, two parts composition includes:

(a) first part (A), the first part (A) containing (methyl) acrylate component, organic peroxide and Free radical curable components containing acetal；And

(b) second part (B), the second part (B) are spread out containing (methyl) acrylate component and benzoylthioureas Biology or benzoylthio carbamate derivatives；

Wherein when mixing and being applied at least one substrate by the first part and second part, the composition To there are most about 5 minutes open hour, and when substrate cooperation, they have about 20 minutes or shorter at 80 DEG C Curing time, and set time less than 5 minutes.

In another aspect, a kind of adhesive composition is provided, described adhesive composition includes:

(a) (methyl) acrylate component；

(b) solidification packaging (curative package), the solidification packaging includes organic peroxide and benzoyl Thiourea derivative or benzoylthio carbamate derivatives；And

(c) the free radical curable components containing acetal.

Specific embodiment

Adhesive composition of the invention is provided to the substrate being made of a variety of materials (many is metal material) The enhancing adhesiveness on surface.

Therefore, the present invention provides adhesive composition, described adhesive composition be sometimes include first part and the Two parts of two parts construct, and the first part contains (methyl) acrylate component, organic peroxide and containing acetal Free radical curable components, and the second part contains (methyl) acrylate component and benzoylthioureas derivative Or benzoylthio carbamate derivatives.

The substrate for realizing enhancing adherency and bond strength is metal base such as mild steel, stainless steel and aluminium, glass baseplate (such as glass baseplate of ink coating) and various plastic basis materials (such as acrylic compounds, polycarbonate, polycarbonate-ABS and Buddhist nun Dragon).

The combination of part (A) composition and part (B) composition, which generates, to be suitable for matching a substrate surface bonding It is bonded to the curable compositions of another substrate surface.One or more substrates can be constructed to form adhesive bond or lamination Part.After solidification, the reaction product of the composition is the bonding between two substrate surfaces.

Although two parts composition can be used for a variety of business applications, they are in electronic display unit such as hand-held It is particularly useful in the assembling of phone and computer installation.

(A) part

(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 C₁-C₁₀Alkyl.

Advantageously, the group is (methyl) acryloxy.Term " (methyl) acryloxy " refers to acrylate Both with methacrylate, wherein R is respectively H or methyl.The dosage that has of (methyl) acrylate component is usually whole group Close the about 20 weight % to about 80 weight % of object.It is desirable that composition of the invention contains about 50 weight % to about 70 weight % (methyl) acrylate component.

(methyl) acrylate component can exist in the form of polymer, monomer or combinations thereof.When with polymer form In the presence of, (methyl) acrylate component can be the polymer chain for being connected at least one above-mentioned group.The group can be with Positioned at the side chain or terminal position or their combination of main chain.It can be advantageous to there are at least two groups, and institute Terminal position can be located at by stating group.(methyl) acrylate component can have by the following polymer chain constituted: poly- Ethylene, polyethers, polyester, polyurethane, polyamide, epoxy resin, vinyl esters, phenolic aldehyde, amino resins, oil base etc., such as this field Technical staff is it is well known that or its random or block combination.

The polymer chain can be formed by the polymerization of vinyl monomer.The illustrative example of this vinyl monomer is (methyl) methyl acrylate, (methyl) acrylic acid, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) propylene Isopropyl propionate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) propylene Sour n-pentyl ester, (methyl) the just own ester of acrylic acid, (methyl) cyclohexyl acrylate, the positive heptyl ester of (methyl) acrylic acid, (methyl) propylene Sour n-octyl, (methyl) 2-EHA, (methyl) nonyl acrylate, (methyl) decyl acrylate, (methyl) propylene Sour dodecyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid toluene base ester, (methyl) benzyl acrylate, (methyl) third Olefin(e) acid 2- methoxy acrylate, (methyl) acrylic acid 3- methoxybutyl, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) octadecyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 2- amino Ethyl ester, γ-(methyl) acryloyloxypropyltrimethoxysilane, (methyl) acrylic acid-ethylene oxide adduct, (methyl) third Olefin(e) 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, (methyl) acrylic acid is enjoyed a double blessing methyl fluoride methyl esters, (methyl) acrylic acid 2- perfluoro-methyl -2- perfluoro-ethyl methyl esters, (methyl) acrylic acid 2- perfluoro hexyl ethyl ester, (methyl) acrylic acid 2- perfluoro decyl ethyl ester, (methyl) acrylic acid 2- perfluor cetyl ethyl ester, ethoxy Base trimethylolpropane trimethacrylate, trimethylol-propane trimethacrylate, five propylene of dipentaerythritol monohydroxy Acid esters, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, 1,6 hexanediol diacrylate, Neopentylglycol diacrylate, pentaerythritol tetraacrylate, 1,2- butanediol diacrylate, trimethylolpropane ethyoxyl Compound three (methyl) acrylate, glyceryl propoxylate three (methyl) acrylate, trimethylolpropane tris (methyl) third Olefin(e) acid ester, dipentaerythritol monohydroxy five (methyl) acrylate, three (propylene glycol) two (methyl) acrylate, neopentyl glycol third Oxygroup compound two (methyl) acrylate, 1,4- butanediol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, Triethylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, Ethoxylated bisphenol A bis- (methyl) acrylic acid Ester.These monomers can be used alone, and multiple monomers in these monomers can also be made to be copolymerized.Especially preferred (methyl) Acrylate monomer includes the monomer that the alcohol part of ester group contains 1-8 carbon atom.For example, 2-Ethylhexyl Methacrylate, Hydroxyethyl methacrylate, cyclohexyl methacrylate, ethyl methacrylate, 1,3 butylene glycol dimethylacrylate (BDMA), butyl methacrylate and methyl methacrylate (MMA) are some examples.

But especially preferably at least one as (methyl) acrylate component of (methyl) tetrahydrofurfuryl acrylate Point.

(A) amount of (methyl) acrylate component used in fraction compositions can be about 20 weight % to about 95 weights Measure %, for example, about 40 weight % to about 75 weight %.

Free radical curable components containing acetal

As the free radical curable components containing acetal, the compound of following general structure can be used:

Wherein R¹It is H, CH₃Or CN；

R²It is multivalence C₁To C₈Alkyl chain, C₆To C₁₂Aryl or C₃To C₈Naphthenic base；And

N is 1-4.

R²It is divalent unsaturation C₂-C₄₀Linker (such as can be derived from dicarboxylic acids, the dicarboxylic acids be selected from maleic acid, Fumaric acid, itaconic acid, glutaconate, traumatic acid, glutinicacid (glutinic acid) and mesaconic acid).

Wherein R¹It is C₁To C₈Alkyl, C₆To C₁₂Aryl or C₃To C₈Naphthenic base；And

R²It is divalent unsaturation C₂-C₆₀Linker (such as can be derived from tricarboxylic acids, the tricarboxylic acids be selected from citric acid, Isocitric acid, aconitic acid and trimesic acid).

The specific example of (methyl) acrylate compounds containing acetal includes following example:

(A) amount of (methyl) acrylate compounds used in fraction compositions containing acetal can be about 1 weight Measure % to about 20 weight %, for example, about 2.5 weight % to about 10 weight %.

Peroxy initiator

It is hydrogen peroxy initiator especially suitable for a kind of peroxy initiator of the invention.Wherein, organic hydroperoxide is outstanding It is applicable in.Particularly preferred organic hydroperoxide includes to methane hydroperoxides, diisopropyl benzene hydroperoxides, firpene (pinene) hydroperoxides, methyl ethyl ketone hydroperoxides, tert-butyl -2- ethoxy peroxide, t-butyl peroxy horse Come sour, cumene hydroperoxide (CHP), tert-butyl hydroperoxide (TBH) and benzoyl peroxide (BP).In addition, also Inorganic peroxide and composition, such as peroxyester, such as peroxidized t-butyl perbenzoate, benzophenone peroxide can be used Change ester and Fluorenone peroxyester, peroxycarbonates, and the chemical combination containing halogen with the electronic structure for promoting free radical to be formed Object is decomposed to form the ester of free radical.Term " peroxide " refers to peroxide, the hydroperoxides for being suitable for preparing anaerobic curing system And peroxyester.

Peroxide polymerization initiator can be to be enough to execute its amount for causing function in (A) fraction compositions.Useful Non-limiting amounts includes the about 0.25 weight % to about 10 weight % based on entire combination object, and is preferably based on whole group Close the about 1 weight % to about 3 weight % of object.

Free radical inhibitors

Radical polymerization inhibitor can be used to prevent premature reaction before mixing in the present invention.

Many radical polymerization inhibitors appropriate are known in fields, and including quinones, hydroquinones, azanol Class, nitroxyl compound class, phenols, amine, aryl amine, quinolines, phenothiazines etc..Particularly useful free radical inhibitors Including quinhydrones, tert-butyl hydroquinone (" TBHQ "), methylnaphthohydroquinone, ethoxy quinhydrones, phenthazine and NAUGARD-R, (alkyl replaces P-phenylenediamine mixture, derive from Crompton Corp.).One or more individual free radical inhibitors can also be combined Component.

(A) amount of free radical inhibitors component used in fraction compositions can be 0 weight % to about 1 weight %, example Such as from about 0.05 weight % to 0.2 weight %.

(B) part

(methyl) acrylate component

(B) (methyl) acrylate component used in part can be (methyl) acrylate used in the part (A) Any one or more of.

(B) amount of (methyl) acrylate component used in fraction compositions can be about 20 weight % to about 95 weights Measure %, for example, about 40 weight % to about 75 weight %.

Reactive acid constituents

Composition of the invention includes acid or acid esters (acid ester).Desirably, this component is only in the part (B).It is suitable When acid or acid esters include phosphoric acid or derivative, phosphate and sulfonic acid or derivative.Preferred reactivity acid constituents is phosphate.

The acid monomers are the acid monomers of free redical polymerization, such as olefinic unsaturated monocarboxylic or polycarboxylic acid, maleic acid And crotonic acid.Desired monomer includes methacrylic acid (" MAA ") and acrylic acid.Reactive acid constituents also adjusts and deceleration thermosetting The curing time of property composition.

Phosphate appropriate includes the phosphate that following formula indicates:

Wherein R herein¹It is H or CH₃, and R²It is H, or by the group of following representation:

Wherein R¹It is H or CH₃.Particularly useful phosphate be with trade name T-MULZ 1228 or HARCRYL 1228 or The hydroxyethyl methacrylate that 1228M sells and (respectively derives from Harcross Chemicals, Kansas City, KS) (" HEMA ") phosphate.It further include that at least one strong acid " reactive hydrogen " group or there is at least one phosphonic acids active hydrogen group (R₁R₂POOH) the structure of (such as hydroxyethanediphosphonic acid, phosphonic acids and derivative), or there is phosphonic acid functional groups or similar acid strength official The oligomer or polymer architecture that can be rolled into a ball.

Reactive acid constituents can account for the about 0.25 weight % to about 15 weight % of entire combination object.

Benzoylthioureas derivative or benzoylthio carbamate derivatives

The benzoylthioureas derivative or benzoylthio carbamate derivatives can be following general formula I

Wherein Z is O or N-R, and wherein R is selected from hydrogen, alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl group, carbonyl, alkylidene (methyl) Acrylate, carboxyl or sulfonic acid foundation or R ' are attached to the direct key of phenyl ring；R ' be selected from hydrogen, alkyl, alkenyl, naphthenic base, Aryl, hydroxyalkyl, hydroxyalkenyl group, alkylene ether, alkenylene ether, carbonyl, alkylidene (methyl) acrylate, carboxyl, nitroso Or sulfonic acid foundation；X be halogen, alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl group, alkoxy, amino, carboxyl, nitroso, sulfonic group, Hydroxyl or halogenated alkyl；And Y is-SO₂NH- ,-CONH- ,-NH- and-PO (NHCONHCSNH₂)NH-；And n is 0 or 1, and And m is 1 or 2.

It shown below more specific general formula structure:

Wherein R and R' is independently selected from hydrogen, alkyl, alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl group, alkylidene (methyl) propylene Perhaps R and R' is collectively formed containing carbocyclic ring or is to be connected to containing heteroatomic ring or R' for acid esters, carbonyl, carboxyl or sulfonic acid foundation The direct key of phenyl ring；X is halogen, alkyl, alkenyl, naphthenic base, hydroxyalkyl, hydroxyalkenyl group, alkoxy, amino, alkylene ether, Asia Alkene ether, alkylidene (methyl) acrylate, carbonyl, carboxyl, nitroso, sulfonic group, hydroxyl or halogenated alkyl；And Y is- SO₂NH- ,-CONH- ,-NH- and-PO (NHCONHCSNH₂)NH-；And n is 0 or 1, and m is 1 or 2.

More precisely, the benzoylthioureas derivative or benzoylthio carbamate derivatives can divide Not in structure I I or IIA:

Wherein R, R ', Z, X, Y and n it is as defined above.

Benzoylthioureas derivative or benzoylthio carbamate derivatives in structure I I and IIA respectively More specific example it is as follows:

Wherein R, X, Y and n are as defined above, and X ' is defined such as X.

Alternatively, benzoylthioureas derivative or benzoylthio carbamate derivatives in structure I can be with It is biform (bisversion), wherein R ' is linker.That is,

Wherein R, R ', X, Y and n it is as defined above, and m is 2.

Even more precisely, benzoylthioureas derivative or benzoylthio carbamate derivatives can be with It is:

Benzoyl morpholine thiocarbamide (BMTU)

Benzoyl octyl thiocarbamide (BOTU)

Benzoylthio diethyl urea (BTDEU)

Benzoylthio dihydroxy ethyl urea (BTDHEU)

Benzoyl tetrahydroquinoline thiocarbamide (BTHQTU)

Benzoylcyclohexan base thiocarbamide (BCHTU)

The double benzoylthioureas (CH bis-BTU) of cyclohexyl

Benzoyl naphtho- sultam thiocarbamide (BNSTU)

Benzoylphenyl hydrazides thiocarbamide (BPHTU)

Benzoylthioureas propyl trimethoxy silicane (BTU-PTS)

BTU-H adduct

BTU-HEMA adduct

BTU- water adduct

BTU-CH adduct

Benzoyl saccharin thiocarbamide (BTU-BS)

Benzoyl diacetayl amide urea (BDU)

The benzoylthioureas derivative or benzoylthio carbamate derivatives can be can be used for enhancing The amount of the bond property of composition is in described adhesive composition.For example, they can be with the pact based on entire combination object The amount of 0.25 weight % to about 10 weight %, for example, about 1 weight % to about 5 weight % exist.

The component used in the part (A) and/or the part (B)

Plasticizer

Plasticizer can be used in any portion in two parts composition or two parts.The plasticizer can be with It contributes to the flexibility of the reactivity part of composition and/or may be used as any liquid of the carrier of the other components of composition Body or soluble compound.Example includes aromatic sulfonamides, aromatic phosphate acid ester, alkyl phosphate, dialkylether aromatic esters, polymerization Plasticizer, dialkyl ether diester, polyethylene glycol di, tricarboxylic ester, polyester resin, aromatic diester, three ester (trimellitic acid of aromatics Ester), aliphatic diester, epoxidised ester, chlorohydrocarbon, aromatic oil, alkylether monoesters, naphthenic oil, alkyl monoester, paraffin oil, silicone oil, two Normal-butyl phthalic acid ester, DI-ISOBUTYL PHTHALATE, di-n-hexyl phthalic acid ester, two n-heptyl O-phthalics Acid esters, two -2- ethylhexyl phthalates, 7c, 9c- phthalic acid ester (straight chain and branching), diisooctyl neighbour benzene two Formic acid esters, linear 6c, 8c, 10c phthalic acid ester, diisononylphthalate, linear 8c-10c phthalic acid ester, Linear 7c-11c phthalic acid ester, diisodecylphthalate, linear 9c-11c phthalic acid ester, double undecyls Phthalic acid ester, diiso decyl glutarate, two -2- ethyl hexyl adipates, two -2- ethylhexylazelates, two - It is 2- ethylhexyl sebacate, di-n-butyl sebacate, diiso decyl adipate ester, triethylene glycol caprate-caprylate, three sweet Alcohol 2 ethyl hexanoic acid ester, dibutoxyethyl adipate ester, dibutoxy ethoxyethyl group adipate ester, dibutoxy ethyoxyl Ethyl formal, dibutoxy ethoxyethyl group sebacate, three -2- ethylhexyl trimellitates, three-(7c-9c (lines Property)) trimellitate, three-(8c-10c (linear)) trimellitates, triethyl phosphate, triisopropyl phenyl phosphate, three fourths Base phosphate, 2- ethylhexyl diphenyl phosphate, trioctyl phosphate, isodecyl diphenyl phosphate triphenyl, The triaryl phosphate of synthesis, three butoxyethyl phosphates, three (- chloroethyl) phosphates, butyl phenyl diphenyl phosphoester, Chlorination organophosphorus ester, cresyl diphenyl phosphate, three (two chloropropyls) phosphates, isopropyl phenyl diphenyl phosphoester, Three-dixylenyl phosphates, tricresyl phosphate, diphenyl octyl phosphate.The combination of plasticizer is useful.

It can be the 0 weight % to about 5 weight % of entire combination object with the whole amount of plasticizer in the composition, such as About 0.1 weight % to about 1 weight %.

Block copolymer

When in use, the block copolymer can be appointing for physical property needed for can aid in disclosed composition What block copolymer.The block copolymer can reside in any portion or two parts in two parts composition In.

The block copolymer rubber can be used butadiene or isoprene and styrene block (such as SBS, SIS, SEBS and SB) building, commercial example be available from Shell Chemical Co. product K RATON D-1116 and other D grades of elastomers of KRATON, the VECTOR 2411IP derived from Dexco.

Tg can be used to be below about 25 DEG C, dissolve in the other elastomers of methacrylate/acrylate monomer to replace For block copolymer rubber.Its example is the homopolymer of epichlorohydrin and its copolymer with ethylene oxide, is available from Zeon Chemicals company, product name HYDRIN；Acrylic rubber pellet, derives from Zeon company, and product name is HYTEMP；Polyisoprene rubber；Polybutadiene rubber；Nitrile rubber；And SBR rubber (butadiene and styrene it is random Copolymer).

Yet other block copolymer is also possible to styrene maleic anhydride copolymer, is expressed from the next:

Wherein, v is 1 to 12；W is 1 to 6；And n is 1 to 50.

Styrene maleic anhydride copolymer is well-known, and some of them can be for example with trade name SMA EF80 Sartomer Company, Inc. purchased from Pennsylvania's Exton.Styrene maleic anhydride copolymer represents benzene second The copolymerization product of alkene and maleic anhydride, and it is characterized in that the alternating block of styrene and maleic anhydride moities.

Amphipathic nature block polymer may be particularly suitable.A Kema (Arkema) is gone out with trade name NANOSTRENGTH Sell amphipathic nature block polymer.There are two types of versions at present for this based block copolymer: SBM and MAM.It is reported that the SBM copolymer It is made of polystyrene, 1,4- polybutadiene and syndiotaxy poly- (methyl methacrylate).

In addition it is also possible to use the polymer being made of polymethyl methacrylate (PMMA) and butyl polyacrylate (PB) Material.Such polymer material is referred to as polymethyl methacrylate-block-butyl polyacrylate-block polymethylacrylic acid Methyl terpolymer (MAM).

As A Kema (Arkema) reports that MAM is a kind of triblock copolymer, by the PB of about 70% PMMA and 30% Composition.MAM is made of different segments, to provide the ability of self assembly on a molecular scale.That is, M is polymerization Object assigns hardness, and A is that polymer assigns resilient nature.

Hard polymer segment tends to dissolve in (methyl) acrylate, and elastomer segment is the poly- (first formed after solidifying Base) acrylate offer toughness.MAM can also enhance engineering properties, without damaging intrinsic physical property.MAM can be with Commercially available from trade name NANOSTRENGTH, there are several different brackets, i.e. E-21 and M-52N at present.

A Kema promotes the development of NANOSTRENGTH product line, it is a kind of acrylic block copolymers, can be with Many Polymers Miscibilities, and according to the saying of manufacturer, most of therein is key industry epoxy resin.Additionally referring to beauty State's patent 6,894,113 (Court), wherein the abstract of the patent of ' 113 is related to a kind of thermosetting material with improvement impact resistance Material.The impact resistance derives from the anti-impact modifier of 1-80%, and it includes S-B- that the anti-impact modifier, which includes at least one, M, the copolymer of B-M and M-B-M block, wherein each block is connected with each other by covalent bond or has intermediate group, among this Group is covalently bonded to another block by a block being covalently bonded in the block and by another, M is that PMMA homopolymer or the copolymer including at least methyl methacrylate of 50 weight %, B and thermosetting resin and M are embedding Section is incompatible, and its glass transition temperature Tg is less than the operating temperature of thermosetting material, and S and thermosetting resin, B are embedding Section is incompatible with M block, and its Tg or melting temperature are greater than the Tg of B.

Another commercially available example of the amphipathic nature block polymer is can be with trade name FORTEGRA 100 purchased from Dow The polyether block copolymer of Chemical Co..FORTEGRA 100 is described as a kind of low viscosity increasing by Dow Chemical Co. Tough dose, designed for the efficient secondary phase (high efficiency second phase) in amine curing epoxy systems.According to report Road, FORTEGRA 100 can provide improved toughness, turn without significant impact final coating or the viscosity of composition, vitrifying Temperature, corrosion resistance, solidification rate or chemical resistance.It is reported that since FORTEGRA 100 is due to being not involved in curable epoxide Reaction, therefore can also be used for preparation standard bisphenol-A and Bisphenol F epoxy system.As secondary phase toughener, 100 quilt of FORTEGRA Publicize into it is effective when with the preparation of the designated volume score of most telolemma or component, it is said that usually in 3 siccative volume % to 8 siccative bodies Product % can be realized toughening effect.

Other block copolymers include simultaneously including hydrophobic and hydrophilic segment or part, the block copolymerization with following general formula Object:

―[(R¹)_v―(R²)_w]_n―

Wherein R herein¹It is independently hydrophobic alkene, such as ethylene, propylene, 1- butylene, 1- hexene, 3- methyl-1-pentene Alkene or 4-methyl-1-pentene or polymerizable hydrophobic aromatic hydrocarbon, such as styrene；Each R²It is hydrophily acid anhydrides, such as maleic acid Acid anhydride；V is 1 to 12；W is 1 to 6；And n is 1 to 50.

Hydrophobic patches can be relative to the ratio between hydrophilic fractions in maleic anhydride of styrene block copolymer At least 2: 1, such as in 3:1 between 12:1.Hydrophilic fractions in block copolymer should include acid anhydrides, such as maleic anhydride. Hydrophobic patches in the block copolymer should include ethylene, propylene, 1- butylene, 1- hexene, 3- Methyl-1-pentene, 4- first At least one of base -1- amylene or styrene.It is desirable that the block copolymer should be using the hydrophily including maleic anhydride It is prepared by segment and hydrophobic patches including styrene.

Amphipathic nature block polymer suitable for this paper, therefore these beauty are shown to the reference of following U.S. patent documents State's patent application is incorporated herein by reference.United States Patent (USP) 7,745,535 (Schmidt) is related to and claimed one kind two Parent's property segmented copolymer, wherein at least one block are the host blocks (profiled block) being made of following item: a) Hydrophilic middle block, the hydrophilic middle block is by being selected from acrylic acid, methacrylic acid and acrylic acid and metering system The salt of acid, ester, one or more monomeric units in acid anhydrides and amide are constituted；Dicarboxylic anhydride；Carboxy ethyl acrylate；And propylene Amide；And b) hydrophobic end blocks, wherein the segmented copolymer is insoluble in water, non-dispersible Yu Shuizhong, also not It is dissolved or dispersed in C_1-3In alcohol.

United States Patent (USP) 7,820,760 (Pham) is related to and is claimed a kind of curable adhesive composition epoxy resin, The composition includes: (a) epoxy resin；(b) amphipathic nature block polymer, the amphipathic nature block polymer include at least one (wherein the immiscible is embedding at least one epoxy resin immiscible block segment for a epoxy miscible block segment Section segment includes at least one polyether structure, condition be the polyether structure of the immiscible block segment contain at least one or Multiple oxyalkylene monomers units at least four carbon atoms)；And (c) at least one curing agent.Two in ' 760 patents Parent's property block copolymer is full polyether block copolymer, such as PEO-PBO diblock copolymer or PEO-PBO-PEO three block are total to Polymers.So when the amount of amphipathic nature block polymer makes the epoxy resin composition in ' 760 patents, and do not have There is the composition epoxy resin of amphipathic ether block copolymers to compare, gained cured epoxy resin adhesive resin composition Adhesive strength increases.

United States Patent (USP) 7,670,649 (Hoyles) is related to and a kind of claimed curable ambient cure is highly filled Coating composition, the composition include: (a) epoxy resin；(b) amphipathic nature block polymer, the amphiphilic block Object contains at least one epoxy miscible block segment, and (wherein the unmixing block segment includes at least one polyethers knot Structure, condition are that the polyether structure of the immiscible block segment contains at least one or more oxyalkylene monomers unit) and The unmixing block segment of at least one epoxy resin；And (c) nitrogen-containing hardener of sufficient amount, for being less than about 60 DEG C of ring Solidify the coating composition at a temperature of border.When the epoxy resin composition, the cured epoxy composite of gained The toughness of object increases.

United States Patent (USP) 6,887,574 (Dean) is related to and a kind of claimed curable fire retarded epoxy resin composition, The composition: include (a) at least one fire retarding epoxide resin；(b) at least one amphipathic nature block polymer；And it is (c) solid Agent.The component is present in the curable compositions with amount appropriate and ratio, so that after hardening, the block is total Polymers is self-assembled into nano-structure morphology, such as vermiculate glues form.It is significantly improved it is reported that resulting cured product has High resistance to fracture；And make it possible to for fire retarding epoxide resin being used in the application for needing resistance to fracture.

No. 2008/0287595 U.S. Patent application (Verghese) is related to a kind of composition, and the composition includes: (1) thermosetting resin, the thermosetting resin be selected from epoxy resin, epoxy vinyl ester resin, unsaturated polyester resin or its Mixture, and (2) are dispersed in the amphipathic simulation copolymer (mock copolymer) in the thermosetting resin.In addition, Additionally provide fibre reinforced plastics (FRP), coating and the composite material prepared by the composition.

2010/008931 international patent application of WO (Turakhia) is related to a kind of structural composite material, the structure composite Block copolymer-toughened dose of materials'use increases the resistance to fracture (toughness) of the structural composite material.The structure composite material Material includes (i) carbon fibre reinforcement and (ii) compositions of thermosetting resin；And the wherein compositions of thermosetting resin Include (a) thermosetting resin and (b) block copolymer-toughened dose of at least one.

International patent application WO 2009/018193 (Verghese) be related to a kind of curable compositions, solidification composition filling and Its forming method, the composition include epoxy resin, curing agent, amphipathic toughener and inorganic nano-filler, wherein described Toughener forms the secondary phase at least one Nano grade size.

Total weight of the block copolymer based on described adhesive composition, usage amount herein can be up to about 50 weight % are desired for 5 weight % to 40 weight %.

The glass transition temperature (Tg) of the block copolymer should be higher than that about 40 DEG C.In one embodiment, described The Tg of block copolymer is about 40 DEG C to about 155 DEG C.

The Tg of polymer is the temperature that polymer becomes fragile while cooling or softens when heated.More precisely, Tg is limited Pseudo- second-order phase transistion, in the pseudo- second-order phase transistion, polymer generates glassy with crystalline material similar of property while cooling Structure.When higher than Tg, polymer softens and can be plastically deformed without being broken.In spite of when Tg is described as polymer " softening temperature ", but polymer lower than Tg at a temperature of start softening the case where it is much.This is because due to many non- The softening of the property of crystalline state polymer, polymer may occur in a temperature range, rather than under single temperature value Occur suddenly.Tg typically refers to the midpoint of this range, even if polymer may start to soften at different temperatures.For the application Purpose, the Tg of polymer refer to by ASTM E-1356 determine value.

It can be the about 5 weight % to about 75 weights of entire combination object with the whole amount of block copolymer in the composition Measure %, for example, about 10 weight % to about 50 weight %.

Other additives

Any one of the two parts or the two parts can contain other additives, such as filler, lubrication Agent, thickener and colorant.The filler provides volume in the case where not sacrificing adhesive intensity, and can be selected from height Or the filler of low-density.Equally, certain fillers, such as silica can assign rheology modified or little particle humidification.City The example sold includes Cab-O-Sil 610 and AEROSIL R8200.

Of particular interest are low density filler, because the density of gained final products is lower than the product without filler, But strength characteristics be not present filler when it is essentially identical.

Equally, core-shell polymer may be desired.The core-shell polymer desirably " nucleocapsid " type graft copolymerization Object, or it is also possible to " no shell " crosslinking rubber-like particles, such as acrylonitrile-butadiene-styrene (ABS) (ABS), methacrylic acid Ester-butadiene-styrene (MBS) and methacrylate-acrylonitrile-butadiene-styrene (MABS).BLENDEX 338 is The ABS powder of general GE Plastics company.

Packaging and mixing

When in the form of two parts prepare when, (A) partially and (B) be partially packaged individually in independent container, such as bottle, tank, In pipe or bucket.

(A) is partially partially mixed with (B) with about 1 to about 10 part (a): about 10 to about 1 part (b) of ratio.It is desirable that (A) ratio partially between the part (B) is about 1 part (A): about 1 part (B).

Mixing nozzle can be used in this two-part mixing, and the mixing nozzle has the fluid input for two kinds of components Mouth executes hybrid manipulation appropriate, and binder combination is assigned directly on surface to be bonded.It is commercially available mixing and Distributor another example is derive from ConProTec, Salem, NH'sThe two parts can also bowl, Hand mix in bucket etc., but operator is necessary to ensure that and is sufficiently mixed.As ensuring to mix complete supplementary means, dye can be used Material or pigment prepare each section, to form the third color upon mixing.For example, a part can have weld, separately A part can have blue dyes, so that upon mixing, integral adhesive composition will be green.

Composition of the invention is excellent adhesive and sealant.After being applied to first surface, the first surface E.g. can be incorporated into sheet metal, piece of cloth or the plastic sheet in laminated material, second surface will cooperate with first surface, and And with adhesive curing, the two surfaces be will combine together.Another advantage is not need surface treatment to bond Clean substrate.

Term " solidification " refers to the chemical reaction in the present invention converting fluid mixture to solid adhesion.The combination The solidification process of object is exothermic, and when using big grain adhesive, solidification temperature is likely to be breached about 120 DEG C or so.

After mixing, described adhesive composition in about 20 minutes at about 80 DEG C, and in room temperature in about 24 hours Under be fully cured.Set time, the load of 3Kg will be supported at this time by bonding in the range of about 7 minutes to about 10 minutes.