CN104119824A - Adhesive composition as well as retro-reflective material and preparation method thereof - Google Patents
Adhesive composition as well as retro-reflective material and preparation method thereof Download PDFInfo
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- CN104119824A CN104119824A CN201410373935.4A CN201410373935A CN104119824A CN 104119824 A CN104119824 A CN 104119824A CN 201410373935 A CN201410373935 A CN 201410373935A CN 104119824 A CN104119824 A CN 104119824A
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Abstract
The invention provides an adhesive composition capable of being cured through cross-linking. The adhesive composition comprises epoxy resin and a flexible polymer capable of being cured together with epoxy resin through cross-linking, wherein the glass transition temperature of the flexible polymer is -20DEG C to -10DEG C, and the molecular weight of the flexible polymer is no less than 10000. The invention further provides a retro-reflective material and a preparation method thereof. The epoxy resin is better in viscosity, and the flexible polymer capable of being cured together with epoxy resin through cross-linking has better flexibility, so that the adhesive composition combines the advantages of the epoxy resin and the flexible polymer; when the adhesive composition is used for preparing the retro-reflective material, glass microbeads and matrix can be adhered together only by less adhesive composition, so that the retro-reflective material has better flexibility and better wearing comfortableness.
Description
Technical field
The present invention relates to retroreflecting light reflecting material field, particularly, relate to a kind of adhesive compound of cross-linkable solidifying, the retroreflecting light reflecting material of adhesive compound that comprises this cross-linkable solidifying and the preparation method of this retroreflecting light reflecting material.
Background technology
Retroreflecting light reflecting material is generally comprised of reflecting layer, the passive base material 100 of granulated glass sphere 300, shiny effect and the adhesive layer 200 that glass microballon is bonded on base material 100, wherein, reflecting layer is arranged on the surface of granulated glass sphere 300 and adhesive layer 200 laminatings, and the two has formed the optical system of retroreflecting.As shown in Figure 1, when Ray Of Light incides described retroreflecting light reflecting material surface, can, through being equivalent to the refraction of glass microballon and the reflection in reflecting layer of sphere lens, get back to light source direction.That is,, when irradiate light is on retroreflecting light reflecting material, reflected light can reflect back by the former input path of incident light (light source).
When people are when carrying out nocturnalism, dress has the clothes of retroreflecting light reflecting material, can produce strong eye-catching effect, thereby can allow motor vehicle driver find in time and take measures, and plays the effect of safeguard protection for wearer.
Had at present multiple retroreflecting light reflecting material, for example, disclose a kind of flexible reflective article in US 4272564, this flexibility reflective article comprises glass microballon, be formed on reflecting layer on glass microballon and the silk ribbon of support glass microballon.Silk ribbon is flexible fabric, when utilizing binding agent that glass microballon is sticked on silk ribbon, often needs a large amount of binding agents, has reduced the flexibility of the flexible reflective article of final acquisition, thereby has reduced level of comfort and the aesthetic feeling of dress.
Therefore the consumption that, how to reduce binding agent when guaranteeing the cohesive strength of glass microballon on base material becomes this area technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the present invention is to provide a kind of adhesive compound of cross-linkable solidifying, the retroreflecting light reflecting material of adhesive compound that comprises this cross-linkable solidifying and the preparation method of this retroreflecting light reflecting material.Utilize less adhesive compound provided by the present invention glass microballon can be bonded on matrix reliably.
To achieve these goals, as one aspect of the present invention, a kind of adhesive compound of cross-linkable solidifying is provided, after described adhesive compound crosslinking curing, there is flexibility, wherein, described adhesive compound comprises epoxy resin and flexible polymer that can be curing with cross linking of epoxy resin, and the second-order transition temperature of described flexible polymer is between-20 ℃ to-10 ℃, and the molecular weight of described flexible polymer is not less than 10000.The adhesive compound of described cross-linkable solidifying also comprises can be by epoxy resin and the curing co-curing agent of the crosslinked polymer based on acrylate.
As another aspect of the present invention, a kind of retroreflecting light reflecting material is also disclosed, this retroreflecting light reflecting material comprises matrix, retroreflecting element layer and described retroreflecting element layer is bonded in to the adhesive layer on described matrix, wherein, the adhesive compound crosslinking curing that described adhesive layer is above-mentioned cross-linkable solidifying provided by the present invention forms.Described matrix is selected from any one in mylar, nylon cloth and polyester-mixed cotton cloth.
As another aspect of the present invention, a kind of preparation method of retroreflecting light reflecting material is disclosed, wherein, described preparation method comprises: reflecting element layer is provided; Matrix is provided; By tackiness agent, described reflecting element layer is bonded on described matrix, to obtain retroreflecting light reflecting material, wherein, described tackiness agent is above-mentioned tackiness agent provided by the present invention.
The viscosity of epoxy resin is better, and flexible polymer that can be curing with cross linking of epoxy resin has good flexibility, adhesive compound provided by the present invention combines the advantage of the two, when the adhesive compound that utilizes described cross-linkable solidifying is prepared retroreflecting light reflecting material, only need less adhesive compound by glass microballon together with bond matrix, to make retroreflecting light reflecting material there is good flexibility and good wearing comfort.
Accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the schematic diagram of retroreflecting light reflecting material.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
As one aspect of the present invention, a kind of adhesive compound of cross-linkable solidifying is provided, after described adhesive compound crosslinking curing, there is flexibility, wherein, described adhesive compound comprises epoxy resin and flexible polymer that can be curing with cross linking of epoxy resin, the second-order transition temperature of described flexible polymer is between-20 ℃ to-10 ℃, and the molecular weight of described flexible polymer is not less than 10000.
Term " epoxy resin " refers to contain in molecule two or two above epoxy group(ing) and under existing, can form the general name of the compound of three-dimensional crosslinking structure at suitable chemical assistant (as solidifying agent).
Because the second-order transition temperature of described flexible polymer is between-20 ℃ to-10 ℃, under room temperature (25 ± 5 ℃) state, described flexible polymer all shows snappiness.Because the molecular weight of described flexible polymer is not less than 10000, that is, described flexible polymer has sizable molecular weight, and therefore, described flexible polymer shows good flexibility.
When adhesive compound solidifies, flexible polymer and cross linking of epoxy resin solidify, and due to the existence of described flexible polymer, make the final curing adhesive layer obtaining have good flexibility.
Utilizing described adhesive compound that granulated glass sphere (is for example bonded in to flexible matrix, mylar, nylon cloth, polyester-mixed cotton cloth etc.) go up while obtaining retroreflecting light reflecting material, the crosslinking curing of epoxy resin and described flexible polymer provides viscosity, granulated glass sphere is bonded on flexible matrix, in addition, the adhesive layer of making due to adhesive compound has good flexibility, and therefore, the retroreflecting light reflecting material of acquisition also has good flexibility.
Further, because the product after described adhesive compound crosslinking curing has good flexibility, therefore, adhesive compound after crosslinking curing can be attached on flexible matrix well, and can be out of shape with the distortion of flexible substrate, that is, the adhesive compound after crosslinking curing can not come off from matrix easily, and then granulated glass sphere can be bonded on flexible matrix reliably.
The adhesive compound of cross-linkable solidifying provided by the present invention can comprise can be by the co-curing agent of epoxy resin and described flexible polymer crosslinking curing.
Certainly, the adhesive compound of cross-linkable solidifying provided by the present invention also can not comprise above-mentioned co-curing agent.In this case, can be when using the adhesive compound of cross-linkable solidifying provided by the present invention, then add above-mentioned co-curing agent in the adhesive compound of described cross-linkable solidifying.
In order to promote the viscosity of the adhesive compound of cross-linkable solidifying provided by the present invention, preferably, the adhesive compound of described cross-linkable solidifying can also comprise coupling agent.After having increased coupling agent, can reduce while utilizing described tackiness agent that granulated glass sphere is bonded on flexible matrix described in the consumption of tackiness agent.In addition, less tackiness agent consumption is also to make one of comparatively soft reason of final retroreflecting light reflecting material.
In the present invention, the specific form of epoxy resin and flexible polymer is not had to special restriction.For example, as a kind of preferred implementation of the present invention, described epoxy resin can comprise bisphenol A type epoxy resin, and described flexible polymer can comprise the polymkeric substance based on acrylate, and the polymericular weight based on acrylate is not less than 20000.
The molecule of bisphenol A type epoxy resin comprises the resin compound of at least two reactive epoxy groups.Bisphenol A type epoxy resin is dihydroxyphenyl propane, epoxy chloropropane condensation under alkaline condition, through washing, the refining macromolecular compound forming of desolventizing.
The macromolecular structure of bisphenol A type epoxy resin has following characteristics: 1) macromolecular two ends are epoxy group(ing) that response capacity is very strong; 2) on molecular backbone chain, having many ehter bonds, is a kind of line style polyether structure; 3) on the molecular resin chain that n value is larger regularly, there are many secondary hydroxyls in apart from each other ground, can regard a kind of long-chain polyhydric alcohol as; 4) on main chain, also have a large amount of phenyl ring, methyne and sec.-propyl.
Each structural unit of bisphenol A type epoxy resin is given resin following functions: 1) epoxy group(ing) and hydroxyl are given resin reaction, makes resin cured matter have very strong force of cohesion and bonding force; 2) ehter bond and hydroxyl are polar groups, contribute to improve wetting property and adhesive power; 3) ehter bond and C-C key make macromole have kindliness; 4) phenyl ring is given polymkeric substance with thermotolerance and rigidity; 5) sec.-propyl also invests the certain rigidity of macromole; 6) bond energy of-C-O-key is high, thereby has improved alkali resistance.
The molecular structure of bisphenol A type epoxy resin has determined that its performance has following characteristics: 1) though bisphenol A type epoxy resin is thermoplastic resin, but can form the cured article of multiple excellent performance with multiple solidifying agent, catalyzer and additive, almost can meet various service requirementss; 2) while solidifying, substantially do not produce small molecules volatile matter, can low pressure molding, can be dissolved in multi-solvents; 3) cured article has very high intensity and bonding strength; 4) cured article has higher erosion resistance and electrical property; 5) cured article has certain toughness and thermotolerance.
Term " polymkeric substance based on acrylate " refers to the polymkeric substance of the ester class of vinylformic acid and homologue thereof.Except increasing the flexible fabric after described adhesive solidification, add the polymkeric substance based on acrylate in the adhesive compound of cross-linkable solidifying, to introduce carboxyl, increase the polarity of the adhesive compound of described cross-linkable solidifying, and further increase the sticking power of the adhesive compound of described cross-linkable solidifying to base material.And molecular weight is not less than 20000 the polymkeric substance based on acrylate and has good flexibility and sticking power preferably concurrently.
As a kind of embodiment of the present invention, the multipolymer of the methacrylic acid monomer that the polymkeric substance based on acrylate comprises one or more methacrylate monomer and contains carboxyl.In order to make flexibility and the adhesivity of described adhesive compound obtain good balance, preferably, the polymkeric substance based on acrylate is 40～50 mass parts at the content of the adhesive compound of described cross-linkable solidifying.As a kind of embodiment of the present invention, described co-curing agent comprises polymeric amide, and the content of polymeric amide is 20～30 mass parts.
When described epoxy resin comprises bisphenol A type epoxy resin, described flexible polymer can also be polyester polyol, and the molecular weight of polyester polyol is greater than 30000.Molecular weight is greater than 30000 polyester polyol and conventionally has good elasticity and flexibility, and therefore, the product forming after polyester polyol and bisphenol A type epoxy resin crosslinking curing also has good flexibility.Preferably, polyester polyol obtains by any both and hexanodioic acid copolymerization in ethylene glycol, butyleneglycol, isoamyl glycol.For example, the polyester polyol that ethylene glycol, butyleneglycol and hexanodioic acid copolymerization obtain; Or, the polyester polyol that butyleneglycol, isoamyl glycol and hexanodioic acid copolymerization obtain; Or, the polyester polyol that ethylene glycol, isoamyl glycol and hexanodioic acid copolymerization obtain.
In the present invention, the content of polyester polyol can be 50～60 mass parts.
When described flexible polymer is polyester polyol, co-curing agent can comprise isocyanate prepolymer, and the molecular structure of this isocyanate prepolymer is with alkyl group side chain-[(CH2)
n]-, wherein, 15≤n≤30, alkyl group side chain-[(CH2)
n]-be flexible side-chains, can be used in the flexibility that increases polyester polyol and the product of bisphenol A type epoxy resin crosslinking curing acquisition.Preferably, the content of isocyanate prepolymer can be 1～10 mass parts.
As noted before, the adhesive compound of described cross-linkable solidifying can also comprise coupling agent.In the present invention, the particular type of coupling agent is not had to special restriction.For example, coupling agent can comprise silane coupling agent.
Term herein " silane coupling agent " is the silicoorganic compound that a class contains two kinds of different chemical character groups in molecule simultaneously, and its classical product can be used general formula YSiX
3represent.In formula, Y is non-hydrolysising group, comprise alkenyl (being mainly vinyl), and end is with Cl, NH
2, SH, epoxy, N
3, the functional group such as (methyl) acryloxy, isocyanate group alkyl, i.e. carbon functional group; X is hydrolysable group, comprises Cl, OM
e(methoxyl group), OEt (ethylene glycol terephthalate), OC
2h
4oCH
3, OSiMe
3and OAc etc.Due to said structure, in its molecule, have simultaneously can and inanimate matter material (as glass, silica sand, metal etc.) chemically combined reactive group and with the chemically combined reactive group of organic material (synthetic resins etc.).
Or described coupling agent can also comprise tetrabutyl titanate.
In order to reduce the cost of the adhesive compound of described cross-linkable solidifying, preferably, the adhesive compound of described cross-linkable solidifying also comprises mineral filler.Mineral filler used herein can comprise any one or a few the mixture in kaolin, diatomite, talcum powder, graphite, carbon black, aluminum oxide powder, glass powder, asbestos powder, mica powder, silica powder, carbon fiber, dust cork, silicon carbide.
As another aspect of the present invention, a kind of retroreflecting light reflecting material is also provided, this retroreflecting light reflecting material comprises flexible matrix, retroreflecting element layer and described retroreflecting element layer is bonded in to the adhesive layer on described matrix, wherein, the adhesive compound crosslinking curing that described adhesive layer is above-mentioned cross-linkable solidifying provided by the present invention forms.
As noted before, utilize the adhesive layer of the adhesive compound crosslinking curing acquisition of cross-linkable solidifying provided by the present invention to have the high and flexible advantage of cohesive strength concurrently.
Particularly, utilizing described adhesive compound that granulated glass sphere (is for example bonded in to flexible matrix, mylar, nylon cloth, polyester-mixed cotton cloth etc.) go up while obtaining retroreflecting light reflecting material, the crosslinking curing of epoxy resin and described flexible polymer provides viscosity, granulated glass sphere is bonded on flexible matrix, and in addition, the adhesive layer of making due to adhesive compound has good flexibility, therefore, the retroreflecting light reflecting material of acquisition also has good flexibility.
Further, because the product after described adhesive compound crosslinking curing has good flexibility, therefore, adhesive compound after crosslinking curing can be attached on flexible matrix well, and can be out of shape with the distortion of flexible substrate, that is, the adhesive compound after crosslinking curing can not come off from matrix easily, and then retroreflecting element layer can be bonded on flexible matrix reliably.
In the present invention, described matrix has flexibility, and preferably, described matrix can be selected from any one in mylar, nylon cloth and polyester-mixed cotton cloth.
In the present invention, term " mylar " refers to by trevira and weaves the cloth forming.Trevira refers to that polyester that organic dibasic acid and dibasic alcohol polycondensation form is through the synthon of spinning gained.
Term " nylon cloth " refers to by nylon wire weaves the cloth forming.Nylon wire refer on molecular backbone chain, contain recurring amide radical group-[NHCO]-the fiber general name made of thermoplastic resin.
Term " polyester-mixed cotton cloth " refers to polyester cotton, take terylene as major ingredient, the textiles that the cotton mixed yarn of employing 65%-67% terylene and 33%-35% is made into.
In the present invention, described retroreflecting element layer comprises a plurality of reflecting elements that are partially submerged in described adhesive layer, described reflecting element comprises granulated glass sphere and is coated in granulated glass sphere and embeds the reflector layer in the part in described adhesive layer, and the diameter of described granulated glass sphere is between 30～100 μ m.Reflector layer is generally the metal level being plated on granulated glass sphere, and conventionally, the thickness of reflector layer can be between 10～500nm.
Preferably, the material of making described reflector layer is selected from any one in aluminium and silver.For cost-saving, conventionally can aluminium make described reflector layer.
Because the tackiness agent of cross-linkable solidifying provided by the present invention has good adhesive property, therefore, use a small amount of tackiness agent can obtain desirable cohesive strength.Conventionally, the thickness of described adhesive layer is between 30 μ m to 45 μ m.
Recurrence radiation light reflecting material provided by the present invention can be for clothes, and for example, shirt, sweater, jacket, trousers, shoes etc. are upper, or described retroreflecting light reflecting material can also be arranged on knapsack.
As another aspect of the present invention, a kind of preparation method of retroreflecting light reflecting material is provided, wherein, described preparation method comprises:
Reflecting element layer is provided;
Matrix is provided;
By tackiness agent, described reflecting element layer is bonded on described matrix, to obtain retroreflecting light reflecting material, wherein, described tackiness agent is above-mentioned tackiness agent provided by the present invention.
In the present invention, matrix can be flexible substrate.Because described tackiness agent is above-mentioned tackiness agent provided by the present invention, therefore, by less consumption, described reflecting element layer can be bonded on described matrix securely.And the adhesive layer forming after described tackiness agent crosslinking curing has good flexibility, make above-mentioned retroreflecting light reflecting material also there is good flexibility, improved the comfort level of utilizing the clothing that above-mentioned retroreflecting light reflecting material makes.
As noted before, reflecting element layer comprises the granulated glass sphere that is provided with reflector layer, described in provide the step of reflecting element layer to comprise:
Granulated glass sphere is fixed on film carrier;
At described granulated glass sphere, deviate from the surface of described film carrier reflector layer is set, to obtain described reflecting element layer.
Correspondingly, by tackiness agent, described reflecting element layer is bonded on described matrix and is comprised to obtain the step of described retroreflecting light reflecting material:
To the surface that is provided with reflector layer on described reflecting element layer, apply described tackiness agent;
Described matrix is attached on described adhesive layer;
Make described adhesive layer crosslinking curing, so that matrix and described reflecting element layer are bondd;
Peel off described film carrier.
In the present invention, the specific form of film carrier is not had to requirement, as long as can fixing glass pearl, and can after matrix and reflecting element layer bonding, peel off with described reflecting element layer.
For example, film carrier can for paper-PET film (, described film carrier comprises paper and is arranged on the PET film on paper), granulated glass sphere is being fixed in the step on film carrier, can first granulated glass sphere be dispersed in equably on PET film surface, then the film carrier that is paper-PET film to form heats, and PET film is melted slightly, and then granulated glass sphere can be sticked on described film carrier.
Or described film carrier can comprise PET film and be arranged on the lip-deep pressure-sensitive adhesive layer of PET film, granulated glass sphere is fixed in the step on film carrier, directly granulated glass sphere is dispersed on pressure-sensitive adhesive layer equably.
Or described film carrier can comprise PE film and be arranged on the lip-deep PET film of PE film.Granulated glass sphere is being fixed in the step on film carrier, can first granulated glass sphere be dispersed in equably on PET film surface, the film carrier that is then PE-PET film to form heats, and PET film is melted slightly, and then granulated glass sphere can be sticked on described film carrier.
Herein, term " PET " refers to polyethylene terephthalate, and term " PE " refers to polyethylene.
Preferably, make described adhesive layer crosslinking curing, so that the step of matrix and described reflecting element layer bonding is comprised:
Described adhesive layer is dried, and drying temperature is 60～80 ℃, and be 1～5min time of drying;
Described matrix is fitted in to hot pressing on the surface of dry described adhesive layer, the temperature of hot pressing is at 70～80 ℃, and the power applying during hot pressing is 3～6kgf, and the lasting time of hot pressing is 30s to 60s.
Described adhesive layer is carried out to dry advantage and be, be convenient to the contraposition between matrix and reflecting element layer, thereby can obtain retroreflecting light reflecting material more attractive in appearance.The object of hot pressing is that granulated glass sphere can be embedded in adhesive layer better, and hot pressing can promote epoxy resin and flexible polymer crosslinking curing in adhesive layer.
In the present invention, to the not restriction of the concrete structure of granulated glass sphere, as long as can realize retroreflecting.For example, the diameter of described granulated glass sphere can be between 30～100 μ m.
As noted before, reflector layer can be the reflector layers such as aluminium lamination or silver layer.Therefore, in described manufacture method, the step that reflector layer is set in part upward on the surface of described granulated glass sphere comprises: to aluminizing in part upward on the surface of described granulated glass sphere or silver-plated, to form described reflector layer.
To aluminizing on granulated glass sphere or silver-plated technique is well known in the art, for example, can utilize vacuum aluminum-plating machine or vacuum plating silver machine to aluminize on granulated glass sphere.
As noted before, described matrix is flexible materials, can be selected from any one in mylar, nylon cloth and polyester-mixed cotton cloth.The thickness of matrix can be not more than 50 μ m.
Embodiment
It should be noted that, in the following embodiments:
Epoxy resin is all purchased from Jiangsu Miki Chemical Co., Ltd, and trade names are SM601;
Polymeric amide is all purchased from mountain peak, Changzhou Chemical Co., Ltd., and trade names are 651#;
Isocyanate prepolymer is all purchased from chemical in Bayer, and trade names are desmodur L-75;
Silane coupling agent is Silane coupling agent KH550.
Embodiment 1
The epoxy resin of 20 mass parts is sneaked in the acrylic resin of 40 mass parts, to obtain mixture, in said mixture, add the polymeric amide of 25 mass parts and the silane coupling agent of 5 mass parts subsequently, stir, to obtain the adhesive compound of cross-linkable solidifying.Wherein, polymeric amide is as co-curing agent; Acrylic resin is the polymkeric substance based on acrylate, and acrylic resin is purchased from 3M China Co., Ltd., and trade names are CSA3050, and the molecular weight of acrylic resin is 400000, and second-order transition temperature is-20 ℃.
Embodiment 2
The epoxy resin of 25 mass parts is sneaked in the acrylic resin of 50 mass parts, to obtain mixture, in said mixture, add the polymeric amide of 20 mass parts and the silane coupling agent of 10 mass parts subsequently, stir, to obtain the adhesive compound of cross-linkable solidifying.Wherein, polymeric amide is as co-curing agent; Acrylic resin is the polymkeric substance based on acrylate, and acrylic resin is purchased from 3M China Co., Ltd., and trade names are CSA3035, and the molecular weight of acrylic resin is 20000, and second-order transition temperature is-15 ℃.
Embodiment 3
The epoxy resin of 25 mass parts is sneaked in the acrylic resin of 45 mass parts, to obtain mixture, in said mixture, add the polymeric amide of 25 mass parts and the silane coupling agent of 5 mass parts subsequently, stir, to obtain the adhesive compound of cross-linkable solidifying.Wherein, polymeric amide is as co-curing agent; Acrylic resin is the polymkeric substance based on acrylate, and acrylic resin is purchased from purchased from the happy Chemical Co., Ltd. of Jinan Kraft, and trade names are CF-3A, and the molecular weight of acrylic resin is 20000, and second-order transition temperature is-10 ℃.
Embodiment 4
The epoxy resin of 35 mass parts is sneaked in the polyester polyol of 60 mass parts, to obtain mixture, in said mixture, add the isocyanate prepolymer of 4 mass parts and the silane coupling agent of 1 mass parts subsequently, stir, to obtain the adhesive compound of cross-linkable solidifying.Wherein, isocyanate prepolymer is as co-curing agent; Polyester polyol is purchased from Jiangsu Xu Chuan chemistry limited-liability company, and trade names are EB 1027, and polyester polyol is polyoxyethylene glycol, the multipolymer of polytetramethylene glycol and hexanodioic acid, and the molecular weight of polyester polyol is 30000, second-order transition temperature is-10 ℃.
Embodiment 5
The epoxy resin of 40 mass parts is sneaked in the polyester polyol of 50 mass parts, to obtain mixture, in said mixture, add the isocyanate prepolymer of 10 mass parts and the silane coupling agent of 1 mass parts subsequently, stir, to obtain the adhesive compound of cross-linkable solidifying.Wherein, isocyanate prepolymer is as co-curing agent.Wherein, isocyanate prepolymer is as co-curing agent; Polyester polyol is purchased from Jiangsu Xu Chuan chemistry limited-liability company, trade names are EBD 40, and polyester polyol is polyoxyethylene glycol, the multipolymer of polytetramethylene glycol and poly-pentanediol and hexanodioic acid, the molecular weight of polyester polyol is 40000, and second-order transition temperature is-20 ℃.
Embodiment 6
On the PE film of the film carrier that S1, the granulated glass sphere uniformly dispersing that is 90 μ m by 40 grams of diameters are paper-PE in form, wherein film carrier is of a size of 45cm * 45cm;
S2, to being provided with the film carrier of glass microballon, heat, glass microballon is sticked on film carrier, wherein, Heating temperature is 60 ℃, and be 5min the duration of heat;
S3, utilize vacuum aluminum-plating machine to aluminize to the granulated glass sphere being arranged on described film carrier, to form reflector layer, the thickness of reflector layer is 10nm;
S4, to being provided with the tackiness agent that the cross-linkable solidifying providing in embodiment 1 is provided on the surface of reflector layer on granulated glass sphere, take and form thickness as the adhesive layer of 30 μ m;
S4, will be provided with the film carrier of adhesive layer and the composition of granulated glass sphere is put into baking oven inner drying, drying temperature is 60 ℃, and be 1min time of drying;
S5, the nylon cloth that is 40g/sqm by thickness are attached on the surface of dry tackiness agent;
S6, nylon cloth is carried out to hot pressing, hot pressing temperature is 80 ℃, and pressure is 6kgf, and the time length is 30s;
S7, peel off film carrier, obtain retroreflecting light reflecting material.
Embodiment 7
Utilize the method in embodiment 6 to prepare retroreflecting light reflecting material, difference is, in step S2, Heating temperature is 80 ℃, and the time length is 1min; Tackiness agent in step S4 is the tackiness agent in embodiment 2; In step S5, matrix is polyester-mixed cotton cloth, and thickness is 45g/sqm; In step S6, hot pressing temperature is 70 ℃, and pressure is 3kgf, and the time length is 60s.
Embodiment 8
Utilize the method in embodiment 6 to prepare retroreflecting light reflecting material, difference is, in step S2, Heating temperature is 65 ℃, and the time length is 3min; Tackiness agent in step S4 is the tackiness agent in embodiment 3; In step S5, matrix is mylar, and thickness is 50g/sqm; In step S6, hot pressing temperature is 75 ℃, and pressure is 5kgf, and the time length is 50s.
Embodiment 9
Utilize the method in embodiment 6 to prepare retroreflecting light reflecting material, difference is, in step S2, Heating temperature is 70 ℃, and the time length is 4min; Tackiness agent in step S4 is the tackiness agent in embodiment 4; In step S5, matrix is polyester-mixed cotton cloth, and thickness is 45g/sqm; In step S6, hot pressing temperature is 80 ℃, and pressure is 6kgf, and the time length is 30s.
Embodiment 10
Utilize the method in embodiment 6 to prepare retroreflecting light reflecting material, difference is, in step S2, Heating temperature is 75 ℃, and the time length is 3min; Tackiness agent in step S4 is the tackiness agent in embodiment 5; In step S5, matrix is polyester-mixed cotton cloth, and thickness is 45g/sqm; In step S6, hot pressing temperature is 75 ℃, and pressure is 4kgf, and the time length is 50s.
Testing method
Respectively the reflective cloth of retroreflecting obtaining in embodiment 6～10 is cut into the rectangular cloth sheet of 30cm * 25cm, utilizes vernier callipers to measure respectively the thickness of retroreflecting light reflecting material 1～5; Then utilize the method in ISO63302A to wash the reflective cloth of retroreflecting obtaining in embodiment 6～10, measure retroreflecting coefficient.
Simply introduce ISO 63302A below.
Object: measure the reflective function of family expenses washing front and back light reflecting material, the washing fastness of judgement light reflecting material.
Equipment: meet ISO 6630 standard particular machine.
Water-washing step:
1) sample is put into washing machine, adding companion's cloth to make total washing weight is 2 ± 0.1kg;
2) add appropriate without phosphorus ECE or IEC washing composition;
3) washing intensity: standard; Wash temperature: 2A program is 60 ± 3 ℃; Water level: 10cm; Washing time: 15min; Rinsing: rinsing is 4 times altogether, water level 13cm, first and second rinsing 3min, third and fourth rinsing 2min; Dry: the 4th rinsing finishes rear drying 5min;
4) according to test request, determine cycle index;
5) dry at 50 ± 5 ℃ after having washed;
6) with observation by light microscope light reflecting material Watch glass pearl, whether come off;
7) measure the impact of retro-reflecting coefficient judgement washing on material intensity of light reflection.
Test result is as shown in table 1.
Table 1
From above-mentioned test result, utilize the retroreflecting light reflecting material granulated glass sphere that adhesive compound provided by the present invention makes by preparation method provided by the present invention to be not easy to come off, and thickness is less, that is, utilize less adhesive compound granulated glass sphere can be bonded on matrix reliably.In addition, with hand, touching in embodiment 6～10 after prepared retroreflecting light reflecting material can perception, and above-mentioned retroreflecting light reflecting material is comparatively soft.
Be understandable that, above embodiment is only used to principle of the present invention is described and the illustrative embodiments that adopts, yet the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (26)
1. the adhesive compound of a cross-linkable solidifying, after described adhesive compound crosslinking curing, there is flexibility, it is characterized in that, described adhesive compound comprises epoxy resin and flexible polymer that can be curing with cross linking of epoxy resin, the second-order transition temperature of described flexible polymer is between-20 ℃ to-10 ℃, and the molecular weight of described flexible polymer is not less than 10000.
2. the adhesive compound of cross-linkable solidifying according to claim 1, is characterized in that, the adhesive compound of described cross-linkable solidifying also comprises can be by the co-curing agent of epoxy resin and described flexible polymer crosslinking curing.
3. the adhesive compound of cross-linkable solidifying according to claim 2, is characterized in that, the adhesive compound of described cross-linkable solidifying also comprises coupling agent.
4. the adhesive compound of cross-linkable solidifying according to claim 3, it is characterized in that, described epoxy resin comprises bisphenol A type epoxy resin, and described flexible polymer comprises the polymkeric substance based on acrylate, and the polymericular weight based on acrylate is not less than 20000.
5. the adhesive compound of cross-linkable solidifying according to claim 4, is characterized in that, the multipolymer of the methacrylic acid monomer that the polymkeric substance based on acrylate comprises one or more methacrylate monomer and contains carboxyl.
6. the adhesive compound of cross-linkable solidifying according to claim 5, is characterized in that, the polymkeric substance based on acrylate is 40～50 mass parts at the content of the adhesive compound of described cross-linkable solidifying.
7. the adhesive compound of cross-linkable solidifying according to claim 4, is characterized in that, described co-curing agent comprises polymeric amide, and the content of polymeric amide is 20～30 mass parts.
8. the adhesive compound of cross-linkable solidifying according to claim 3, is characterized in that, described epoxy resin comprises bisphenol A type epoxy resin, and described flexible polymer comprises polyester polyol, and the molecular weight of polyester polyol is greater than 30000.
9. the adhesive compound of cross-linkable solidifying according to claim 8, is characterized in that, polyester polyol obtains by any both and the hexanodioic acid copolymerization in ethylene glycol, butyleneglycol, isoamyl glycol.
10. the adhesive compound of cross-linkable solidifying according to claim 8, is characterized in that, the content of polyester polyol is 50～60 mass parts.
The adhesive compound of 11. cross-linkable solidifyings according to claim 8, is characterized in that, described co-curing agent comprises isocyanate prepolymer, and the molecular structure of this isocyanate prepolymer is with alkyl group side chain-[(CH2)
n]-, wherein, 15≤n≤30.
The adhesive compound of 12. cross-linkable solidifyings according to claim 11, is characterized in that, the content of isocyanate prepolymer is 1～10 mass parts.
13. according to the adhesive compound of the cross-linkable solidifying described in any one in claim 3 to 12, it is characterized in that, described coupling agent comprises silane coupling agent, and the content of silane coupling agent is 3～10 mass parts; Or described coupling agent comprises tetrabutyl titanate.
14. according to the adhesive compound of the cross-linkable solidifying described in any one in claim 3 to 12, it is characterized in that, the adhesive compound of described cross-linkable solidifying also comprises mineral filler.
15. 1 kinds of retroreflecting light reflecting materials, this retroreflecting light reflecting material comprises flexible matrix, retroreflecting element layer and described retroreflecting element layer is bonded in to the adhesive layer on described matrix, it is characterized in that, described adhesive layer is that the adhesive compound crosslinking curing of the cross-linkable solidifying described in any one in claim 1 to 14 forms.
16. retroreflecting light reflecting materials according to claim 15, is characterized in that, described matrix is selected from any one in mylar, nylon cloth and polyester-mixed cotton cloth.
17. according to the retroreflecting light reflecting material described in claim 15 or 16, it is characterized in that, described retroreflecting element layer comprises a plurality of reflecting elements that are partially submerged in described adhesive layer, described reflecting element comprises granulated glass sphere and is coated in granulated glass sphere and embeds the reflector layer in the part in described adhesive layer, and the diameter of described granulated glass sphere is between 30～100 μ m.
18. retroreflecting light reflecting materials according to claim 17, is characterized in that, the thickness of described reflector layer is between 10～500nm.
19. retroreflecting light reflecting materials according to claim 18, is characterized in that, the material of making described reflector layer is selected from any one in aluminium and silver.
20. according to the retroreflecting light reflecting material described in claim 15 or 16, it is characterized in that, the thickness of described retroreflecting light reflecting material is between 100 μ m to 140 μ m.
21. retroreflecting light reflecting materials according to claim 20, is characterized in that, the thickness of described adhesive layer is between 30 μ m to 45 μ m.
The preparation method of 22. 1 kinds of retroreflecting light reflecting materials, is characterized in that, described preparation method comprises:
Reflecting element layer is provided;
Matrix is provided;
By tackiness agent, described reflecting element layer is bonded on described matrix, to obtain retroreflecting light reflecting material, wherein, described tackiness agent is the tackiness agent described in any one in claim 1 to 14.
23. preparation methods according to claim 22, is characterized in that, described in provide the step of reflecting element layer to comprise:
Granulated glass sphere is fixed on film carrier;
At described granulated glass sphere, deviate from the surface of described film carrier reflector layer is set, to obtain described reflecting element layer;
By tackiness agent, described reflecting element layer is bonded on described matrix and is comprised to obtain the step of described retroreflecting light reflecting material:
To the surface that is provided with reflector layer on described reflecting element layer, apply described tackiness agent, to form adhesive layer;
Described matrix is attached on described adhesive layer;
Make described adhesive layer crosslinking curing, so that matrix and described reflecting element layer are bondd;
Peel off described film carrier.
24. preparation methods according to claim 23, is characterized in that, described manufacture method is carried out before being also included in described matrix being attached on described adhesive layer:
Described adhesive layer is dried, and drying temperature is 60～80 ℃, and be 1～5min time of drying;
Make described adhesive layer crosslinking curing, so that the step of matrix and described reflecting element layer bonding is comprised:
Described matrix is fitted in to hot pressing on the surface of dry described adhesive layer, the temperature of hot pressing is at 70～80 ℃, and the power applying during hot pressing is 3～6kgf, and the lasting time of hot pressing is 30s to 60s.
25. according to the preparation method who requires in right described in 23, it is characterized in that, the diameter of described granulated glass sphere is between 30～100 μ m.
26. preparation methods according to claim 23, is characterized in that, the step that reflector layer is set in part upward on the surface of described granulated glass sphere comprises: to aluminizing in part upward on the surface of described granulated glass sphere or silver-plated, to form described reflector layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410373935.4A CN104119824B (en) | 2014-07-31 | Adhesive compound, retroreflecting reflectorized material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410373935.4A CN104119824B (en) | 2014-07-31 | Adhesive compound, retroreflecting reflectorized material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104119824A true CN104119824A (en) | 2014-10-29 |
| CN104119824B CN104119824B (en) | 2016-11-30 |
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| CN105672033A (en) * | 2016-02-01 | 2016-06-15 | 杭州杭化哈利玛化工有限公司 | Modified PAE (polyamide epichlorohydrin resin) coating waterproof agent and preparation method thereof |
| CN108026424A (en) * | 2015-09-15 | 2018-05-11 | 3M创新有限公司 | Adhesive composition and the product being produced from it |
| CN109762499A (en) * | 2019-01-23 | 2019-05-17 | 黑龙江省科学院石油化学研究院 | A kind of nitrile rubber bonding preparation method and application of room temperature curing high-toughness epoxy resin |
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| CN1632024A (en) * | 2004-12-22 | 2005-06-29 | 华南理工大学 | Structural pressure-sensitive adhesive |
| JP2010265440A (en) * | 2009-04-15 | 2010-11-25 | Emulsion Technology Co Ltd | Ultraviolet-curable adhesive composition |
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| CN1074470A (en) * | 1992-01-16 | 1993-07-21 | 中国林业科学研究院林产化学工业研究所 | The manufacture method of acrylic acid adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108026424A (en) * | 2015-09-15 | 2018-05-11 | 3M创新有限公司 | Adhesive composition and the product being produced from it |
| CN105672033A (en) * | 2016-02-01 | 2016-06-15 | 杭州杭化哈利玛化工有限公司 | Modified PAE (polyamide epichlorohydrin resin) coating waterproof agent and preparation method thereof |
| CN109762499A (en) * | 2019-01-23 | 2019-05-17 | 黑龙江省科学院石油化学研究院 | A kind of nitrile rubber bonding preparation method and application of room temperature curing high-toughness epoxy resin |
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