CN120775543A - Composite adhesive for reflective cloth material and preparation method and application thereof - Google Patents
Composite adhesive for reflective cloth material and preparation method and application thereofInfo
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- CN120775543A CN120775543A CN202511207873.4A CN202511207873A CN120775543A CN 120775543 A CN120775543 A CN 120775543A CN 202511207873 A CN202511207873 A CN 202511207873A CN 120775543 A CN120775543 A CN 120775543A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/341—Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0276—Polyester fibres
- B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/06—Vegetal fibres
- B32B2262/062—Cellulose fibres, e.g. cotton
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/416—Reflective
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明公开了一种用于反光布材料的复合胶及其制备方法与应用，包括聚氨酯基体，聚氨酯基体包括羧酸单体；羧酸单体为羟基酸或二元酸，用于在聚氨酯分子链中引入端位羧基。本发明通过上述设计，既保留了聚氨酯基体优异的耐水洗性能，又通过羟基酸或二元酸引入的端位羧基，全面提升了与镀铝层、布基及玻璃微珠的结合牢度，同时增强了交联密度和内聚强度。相比现有技术，本发明有效解决了丙烯酸类复合胶耐水洗性差、传统聚氨酯类复合胶折叠处易磨损脱层的问题，使反光布在经过多次水洗、干洗或工业洗涤后，仍能保持较高的逆反射系数、光滑的表面状态及折叠处的完整性，满足反光服等可穿戴反光材料的严苛使用要求。The present invention discloses a composite adhesive for reflective fabric materials, its preparation method, and application. The composite adhesive comprises a polyurethane matrix, which includes a carboxylic acid monomer; the carboxylic acid monomer is a hydroxy acid or a dibasic acid, which is used to introduce terminal carboxyl groups into the polyurethane molecular chain. Through this design, the present invention not only retains the excellent water-washing resistance of the polyurethane matrix, but also comprehensively improves the bonding strength with the aluminum coating, the fabric base, and the glass microbeads through the terminal carboxyl groups introduced by the hydroxy acid or dibasic acid, while also enhancing the crosslinking density and cohesive strength. Compared with the existing technology, the present invention effectively solves the problems of poor water-washing resistance of acrylic composite adhesives and the easy wear and delamination at the folds of traditional polyurethane composite adhesives. This allows the reflective fabric to maintain a high retroreflective coefficient, a smooth surface state, and the integrity of the folds after multiple washings, dry cleanings, or industrial washings, meeting the stringent use requirements of wearable reflective materials such as reflective clothing.
Description
Technical Field
The invention relates to the technical field of composite glue, in particular to composite glue for a reflective cloth material, and a preparation method and application thereof.
Background
With the rapid promotion of urban construction in China, the reflective material can realize high-efficiency reflection under the irradiation of light rays by virtue of the unique light retroreflection property, so that obvious warning, marking and decoration functions are exerted, and the reflective material becomes an important class for guaranteeing public safety and expanding the application of functional materials. At present, the reflective material is widely applied to the fields of railways, fire protection, buildings, road traffic and the like, and the recognition degree in a low-visibility environment is effectively improved by endowing traffic safety facilities, protective equipment and the like with reflective characteristics, so that key guarantee is provided for the trip safety of personnel and vehicles.
In recent years, with the increasing demand for movable safety protection, reflective materials gradually expand from the fields of stationary building facilities, traffic signs and the like to wearable equipment, wherein reflective clothing has the characteristics of safety protection, attractive appearance, practicability and the like, and becomes a research and development hot spot in the clothing field. The core performance of the reflective clothing depends on the quality of the reflective cloth, the performance of the reflective cloth depends on the used composite adhesive to a great extent, the composite adhesive needs to be firmly combined with a cloth base and a reflective layer, and the severe use requirements of water washing resistance, wear resistance, folding resistance and the like are met, so that the reflective cloth can maintain stable retroreflective performance after long-term use and repeated washing.
In the prior art, the composite glue for the reflective cloth is mainly divided into acrylic resin and polyurethane resin. The acrylic resin composite adhesive is applied to partial scenes, but has the common problems of general washing resistance and insufficient bonding strength with cloth base, and is difficult to meet the use requirements of products such as reflective clothing which need frequent washing.
In contrast, the polyurethane resin composite adhesive has more excellent washing resistance potential due to the molecular structure characteristic, but has the obvious defect in practical application that the existing polyurethane composite adhesive has insufficient bonding fastness with reflective cloth, particularly has serious performance at folding positions, and is easy to generate abrasion and delamination at the folding positions in the washing, dry cleaning or industrial washing processes. There is a need for an improvement to the above-described problems.
Disclosure of Invention
Aiming at the defects of general washing resistance, insufficient bonding strength with cloth base and the like in the prior art, the invention provides a novel composite adhesive for a reflective cloth material, and a preparation method and application thereof.
In order to solve the technical problems, the invention is realized by the following technical scheme:
A composite adhesive for reflecting cloth material is composed of polyurethane matrix containing carboxylic acid as hydroxy acid or binary acid for introducing terminal carboxyl in polyurethane molecular chain.
The polyurethane matrix has excellent water-washing resistance, provides good basic water-resistant characteristic for the composite adhesive, can meet the basic water-resistant requirement of the reflective cloth in a frequent washing scene, and solves the problem of insufficient water-washing resistance of the existing acrylic resin composite adhesive. The introduction of carboxylic acid monomer provides reactive carboxyl functional group for polyurethane molecular chain, creates condition for the subsequent promotion of the binding force of the composite adhesive and the components of the reflective cloth, and breaks through the defect of insufficient binding fastness caused by the lack of effective reactive functional group of the existing polyurethane composite adhesive. Hydroxyl acid or dibasic acid is used as carboxylic acid monomer, and carboxyl can be introduced into the chain end of polyurethane molecule effectively and stably. The terminal carboxyl can react with the aluminized layer to form an ionic bond, so that the bonding fastness of the composite adhesive and the aluminized layer is obviously enhanced, the terminal carboxyl can form a covalent bond with an epoxy cross-linking agent and a silane coupling agent, the bonding strength of the composite adhesive, glass beads and cloth base is improved, the falling off in the washing process is reduced, the crosslinking density can be improved by the reaction of the carboxyl and an epoxy curing agent, the cohesive strength and the solvent resistance of the composite adhesive are improved while the flexibility is ensured, and the wear resistance and the delamination resistance of the folded part are effectively improved.
Through the design, the polyurethane substrate has excellent washing resistance, and the terminal carboxyl introduced by hydroxy acid or dibasic acid has the advantages of comprehensively improving the binding fastness with an aluminized layer, a cloth base and glass beads, and enhancing the crosslinking density and cohesive strength. Compared with the prior art, the invention effectively solves the problems of poor water washing resistance of the acrylic composite adhesive and easy abrasion and delamination at the folding position of the traditional polyurethane composite adhesive, so that the reflective cloth can still maintain higher retroreflection coefficient, smooth surface state and integrity at the folding position after being washed by water, dry cleaning or industry for many times, and meets the severe use requirements of wearable reflective materials such as reflective clothing and the like.
Preferably, the composite adhesive for the reflective cloth material is prepared by polymerizing polyester polyol, diisocyanate, a chain extender, a carboxylic acid monomer, a catalyst, an antioxidant and a solvent in a mass ratio of 36-42:5-7:1-3:1-2:0.12-0.14:0.01-0.02:43-57.
The range of proportions of polyester polyol provides a basic skeleton for the polyurethane matrix, which as a soft segment can impart suitable flexibility and mechanical properties to the composite glue. The proportion range can ensure that the composite adhesive has good ductility after film formation, meets the deformation requirements of the reflective cloth in the use fields of folding, bending and the like, provides a structural foundation for the subsequent penetration combination with a cloth base, and solves the problem that the folding part of the existing polyurethane adhesive is easy to crack due to insufficient flexibility.
The diisocyanate is used as a hard segment raw material, the proportion range of the diisocyanate can ensure that a moderate cross-linking structure is formed with polyester polyol, so that not only the brittleness increase (easy abrasion in washing) of a glue layer caused by the too high proportion is avoided, but also the insufficient cross-linking caused by the too low proportion (influence on the water washing resistance) is prevented, the polyurethane chain segment formed in the proportion range can balance the hardness and the toughness, the basic solvent resistance and the structural stability are provided for the composite glue, and the problem of the insufficient washing resistance or the insufficient wear resistance caused by the unbalance of the cross-linking of the conventional polyurethane glue is solved.
The chain extender is used for adjusting the molecular chain length of polyurethane, the proportion range of the chain extender can control the molecular weight at a moderate level, the molecular chain length can be ensured to be enough to permeate the fabric fibers (the bonding area is increased), and meanwhile, the viscosity abnormality caused by overlong chain is avoided (the coating processing is influenced), so that the bonding fastness of the composite adhesive and the cloth base is enhanced, and the problem of poor cloth base bonding force caused by the improper molecular weight of the existing adhesive is solved.
The proportion range of the carboxylic acid monomer can introduce a proper amount of terminal carboxyl into the polyurethane molecular chain, on one hand, the carboxyl can form an ionic bond with an aluminized layer and form a covalent bond with a silane coupling agent to promote the binding force between the composite adhesive and a reflective fabric key layer (aluminized layer and glass beads), and on the other hand, the proportion range can avoid the hydrophilic increase of the adhesive layer (influence on the water washing resistance) caused by excessive carboxyl or the unobvious increase of the binding force caused by insufficient carboxyl, thereby solving the problem that the binding fastness and the water resistance of the existing polyurethane adhesive are difficult to be compatible due to the unbalance of the carboxyl content.
The proportion range of the catalyst can accurately regulate and control the polymerization reaction rate, thereby ensuring that the reaction is fully carried out (avoiding the influence on the performance by the residual unreacted monomers) and preventing the broadening of the molecular weight distribution (ensuring the narrower molecular weight distribution) caused by the too fast reaction. The polyurethane molecular chains in the proportion range are distributed more uniformly, and the structural consistency of the adhesive layer is higher, so that the stability in the washing-resistant process is improved, and the problem of performance fluctuation of the existing adhesive caused by poor reaction control is solved.
The proportion range of the antioxidant can effectively inhibit the oxidative degradation of the polyurethane chain segments in the processing and using processes, prolong the service life of the composite adhesive, improve the performance stability of the reflective cloth in the environments of long-term illumination, high-temperature washing and the like on the premise of not influencing other performances (such as crosslinking density) of the adhesive layer, and solve the problem that the retroreflection coefficient of the traditional adhesive is attenuated too fast due to oxidative aging.
The proportion range of the solvent can adjust the viscosity of the composite adhesive to be proper under the condition of high solid content, so that the glue solution has good fluidity (being convenient for uniformly covering the bead-planting film and penetrating the cloth base) during coating, and the defect of insufficient solid content (influencing the thickness of the glue layer and the bonding strength) caused by excessive solvent is avoided. The processing suitability of the composite adhesive in the proportion range is better, the composite adhesive can be efficiently compounded with a cloth base, and the problems of uneven coating or insufficient combination caused by improper viscosity of the existing adhesive are solved.
The mass ratio of the components can accurately control the molecular weight (moderate) and the molecular weight distribution (narrower) of the polyurethane matrix through synergistic effect, adapt to the use scene and ensure the proper viscosity under high solid content.
Preferably, the composite adhesive for the reflective cloth material is a mixture of PEA, PDA, PNBA with molecular weight of 2000 and a mass ratio of 3.5-4.5:0.5-1.5:0.5-1.5, diisocyanate is a mixture of TDI-80, HDI and MDI-50 with a mass ratio of 2.5-3.5:1:1, a chain extender is a mixture of BDO and DEG with a mass ratio of 1.5-2.5:1, a carboxylic acid monomer is one of anhydrous oxalic acid, malonic acid, 1, 4-succinic acid and 1, 6-adipic acid, a catalyst is a mixture of organic bismuth and TEDA with a mass ratio of 1:1, and a solvent is a mixture of butanone, ethyl acetate and cyclohexane with a mass ratio of 25-30:14-19:4-8.
The molecular weights of PEA (polyethylene glycol adipate), PDA (polypropylene glycol adipate) and PNBA (butanediol, neopentyl glycol and adipic acid copolymer) are 2000, and the aliphatic polyester polyol can provide a stable soft segment structure and better elasticity and flexibility. TDI-80 (80% 2, 4-toluene diisocyanate), HDI (hexamethylene diisocyanate) and MDI-50 (50% 4,4' -diphenylmethane diisocyanate) are used as diisocyanate, and have moderate reactivity, and can form stable hard segment structure when reacting with polyester polyol. BDO (1, 4-butanediol) and DEG (diethylene glycol) are used as micromolecular dihydric alcohol chain extenders, and the length of polyurethane molecular chains can be accurately regulated, wherein the linear structure of the chain extender can effectively prolong the molecular chains, and meanwhile, the chain extender can form a regular chain segment structure with polyester polyol and diisocyanate, so that the moderate molecular weight is ensured. The anhydrous oxalic acid, malonic acid, 1, 4-succinic acid and 1, 6-adipic acid can stably introduce carboxyl at the chain end of polyurethane molecules due to the reactivity, and the reactivity is adaptive to a polyurethane polymerization system. The organic bismuth catalyst is environment-friendly, has mild reaction and can reduce side reaction, and the TEDA (triethylenediamine) is a strong alkaline catalyst and can accelerate the reaction of isocyanate and hydroxyl. The mixing of the two components in the ratio of 1:1 can accurately regulate and control the polymerization reaction rate. The mixing of the three solvents can optimize the reaction process and the dissolution and coating performances of the composite adhesive, the butanone dissolution capability is strong, the polyester polyol, the diisocyanate and the dihydric alcohol chain extender can be guaranteed to be fully dissolved, the volatilization rate of the ethyl acetate is moderate, the leveling of an adhesive layer is facilitated, and the cyclohexane can reduce the hydrogen bond association generated by the solvents, the polyester polyol and the diisocyanate in the reaction process and guarantee the reaction rate.
The preparation method of the composite adhesive for the reflective cloth material comprises the following steps:
S1, solvent dehydration, namely adding a calcium oxide dehydrator into a solvent to remove water, then separating the solvent from the calcium oxide dehydrator, and sealing and preserving the solvent;
s2, dewatering polyester polyol, namely adding the polyester polyol into a reaction kettle, heating to 105-115 ℃, dewatering for 1h under negative pressure, and sealing and cooling to 65 ℃;
s3, preparing a solution, namely dissolving part of diisocyanate in part of solvent to obtain a solution A, and dissolving a chain extender in part of solvent to obtain a solution B;
s4, in the first stage of polymerization, adding an antioxidant, residual diisocyanate and part of solvent into a reaction kettle, reacting for 30min at 65-80 ℃, then dropwise adding the solution A for 30-90 min, keeping the previous temperature, adding part of catalyst and part of solvent, and reacting for 120min at the temperature;
s5, a second stage of polymerization, namely adding carboxylic acid monomers into a reaction kettle, flushing with partial solvent, reacting for 10min at 65-80 ℃, then dropwise adding solution B for 30-60 min, maintaining the previous temperature, adding the rest catalyst and partial solvent, and reacting for 210min under heat preservation;
And S6, adjusting and discharging, namely cooling to 40 ℃, adding the residual solvent, and uniformly stirring to obtain the composite adhesive solution.
In step S1, if the solvent contains moisture, side reactions (such as urea bond formation or carbon dioxide formation) can occur with diisocyanate, so that polyurethane molecular chains are broken or bubbles are generated, and the adhesive layer structure is destroyed. The calcium oxide dehydrator is used for efficiently removing water in the solvent, and is sealed and stored to avoid secondary water absorption, so that the interference of side reaction can be avoided, the stability of subsequent polymerization reaction is ensured, and a foundation is laid for forming polyurethane matrix with narrow molecular weight distribution.
In step S2, a trace amount of moisture in the polyester polyol also reacts with diisocyanate, resulting in a broadened molecular weight distribution. The free water and the combined water in the polyol can be removed rapidly under the conditions of high temperature and negative pressure, the water removal time of 1h ensures thorough water removal, the water in the air can be prevented from being absorbed again in the cooling process when the temperature is reduced to 65 ℃ in a sealing way, and the dryness of the polyol is ensured. Thus avoiding abnormal polymerization caused by moisture, ensuring the reaction of polyester polyol and diisocyanate to be carried out according to expectations and ensuring the regularity of polyurethane molecular chains.
And S3, respectively dissolving diisocyanate and a chain extender into solutions, so that the concentration of the diisocyanate and the chain extender can be reduced, the dispersibility is improved, and the sudden aggregation caused by overhigh local concentration in the subsequent dripping process is avoided. The solution state ensures that the raw materials are distributed more uniformly in the reaction system, and the reaction rate can be accurately controlled in the dripping process, so that the growth rhythm of polyurethane molecular chains is regulated and controlled stably, and a structure with moderate molecular weight and narrower distribution is formed.
And S4, firstly adding an antioxidant, residual diisocyanate and part of solvent, pre-reacting for 30min, dispersing the antioxidant in advance, inhibiting the oxidative degradation of polyester polyol and diisocyanate at high temperature (protecting the integrity of molecular chains), dropwise adding a solution A at 65-80 ℃ for 30-90 min, slowly dropwise controlling the reaction rate of the diisocyanate and the polyester polyol at low temperature, avoiding local overheating (preventing the breakage of molecular chains or the excessive crosslinking) caused by excessively concentrated heat release of the reaction, adding part of catalyst and preserving heat for 120min, promoting the reaction to be fully carried out, and laying a stable chain segment foundation for the subsequent introduction of carboxyl groups and chain extension. And step S4, through accurate temperature control and time control, the controllability of the polymerization in the first stage is ensured, and the problem of over-wide molecular weight distribution is avoided.
And S5, adding carboxylic acid monomers, then flushing with a part of solvent, fully bringing the carboxylic acid monomers remained on the inner wall of the reaction kettle into the system, ensuring that the carboxylic acid monomers fully participate in the reaction, ensuring the introduction amount of terminal carboxyl groups, reacting for 10min at 65-80 ℃, ensuring the reaction activity of the carboxylic acid monomers and the prepolymer, ensuring that the carboxyl groups are stably grafted on the chain ends of molecules, dripping solution B for 30-60 min, preserving heat for 210min, controlling the chain extension rate by slowly dripping at a controlled temperature, enabling the molecular chains to be uniformly increased to the target length, and simultaneously further promoting the reaction to be complete by the residual catalyst, and ensuring that isocyanate groups are completely reacted.
And S6, adding the residual solvent after cooling to 40 ℃, so that the sudden rise of the viscosity of the glue solution caused by too fast volatilization of the solvent at high temperature can be avoided, the uniform dispersion of the solvent is ensured, the viscosity of the composite glue solution is finally regulated to be suitable under the condition of high solid content, the subsequent coating processing is facilitated, the uniformity of the final product is ensured after uniform stirring, and the local performance fluctuation is avoided.
The whole process of the preparation of the composite adhesive is controllable through the synergistic effect.
Preferably, in the preparation method of the composite adhesive for the reflective cloth material, in the step S3, the solution A consists of 4-5 parts of diisocyanate, 3.5-4.8 parts of butanone and 2-3.5 parts of cyclohexane, and the solution B consists of 1-3 parts of chain extender, 1.5-2.2 parts of butanone and 4-7 parts of ethyl acetate.
The range of parts of diisocyanate in solution a is to precisely match the reaction requirements of the polyester polyol. The butanone has strong dissolving capacity, can ensure the diisocyanate to be fully dissolved, and the cyclohexane can reduce the hydrogen bond association generated by the solvent and the polyester polyol and the diisocyanate in the reaction process, thereby ensuring the reaction rate. The proportion range can ensure that diisocyanate is uniformly dispersed in the solution. In the solution B, the part range of the chain extender is the key for adjusting the molecular chain length of polyurethane, and the molecular chain growth degree can be accurately controlled. Butanone can be used for efficiently dissolving the chain extender, the volatilization rate of ethyl acetate is gentle, and the proportion range can ensure that the chain extender is uniformly dispersed in the solution. The precise dispersion and controllable reaction of key raw materials (diisocyanate and chain extender) in a reaction system are realized through the synergistic effect of the component parts of the solution A and the solution B.
In the step S4, the residual diisocyanate added at first is 1-2 parts, the antioxidant is 0.01-0.02 part, the partial solvent is 1.2-2.5 parts of cyclohexane, the partial catalyst is 0.04-0.05 part, and the partial solvent is 0.8-2 parts of cyclohexane.
The precise regulation and control of the polymerization in the first stage are realized through the synergistic effect of the part ranges of the components in the step S4. The rest diisocyanate is matched with diisocyanate in the solution A to ensure the proportion balance of hard segments, avoid the brittleness or insufficient crosslinking of a glue layer, ensure the accurate dosage of the antioxidant, effectively inhibit oxidative degradation and protect the integrity of molecular chains, ensure the staged addition of cyclohexane, stabilize the viscosity of a system and the dispersibility of raw materials, avoid the out-of-control of local reaction, and ensure the narrow molecular weight distribution by the staged addition of a catalyst, control the reaction rate and ensure the low molecular weight distribution.
Preferably, in the preparation method of the composite adhesive for the reflective cloth material, in the step S5, 2-3 parts of butanone is used as a part of solvent for flushing, 0.08-0.09 parts of residual catalyst is added, 0.1-0.5 parts of butanone is used as a part of solvent, and 17.9-19.5 parts of butanone and 10-12 parts of ethyl acetate are added in the step S6.
The part ranges of the components in the step S5 realize the full utilization of raw materials in the preparation process of the composite adhesive, uniform and controllable reaction and stable product performance through synergistic effect. The butanone flushing ensures complete reaction of carboxylic acid monomers, ensures accurate introduction of carboxyl at the terminal positions, strengthens the binding force of each layer of the composite adhesive and the reflective cloth, ensures the uniformity of polymerization reaction due to the cooperation of the residual catalyst and the butanone, maintains narrow molecular weight distribution, improves the structural stability of an adhesive layer, ensures the processing suitability due to the accurate adjustment of the final viscosity of the residual mixed solvent, and promotes the full combination of the composite adhesive and the cloth base.
An application of the composite adhesive for the reflective cloth material, which is an application of the composite adhesive and the cloth base.
The composite glue and the cloth base are applied in a composite way, so that the comprehensive improvement of the performance of the reflective cloth is realized. The high binding fastness characteristic of the composite adhesive is matched with the fiber structure of the cloth base, the problems that the binding fastness of the composite adhesive and the cloth base is poor, and the folding part is easy to abrade and delaminate in the washing process in the prior art are solved, the composite adhesive is excellent in washing resistance and solvent resistance, so that the compounded reflective cloth can still keep higher retroreflection coefficient, smooth surface and folding part integrity after being washed by family washing, dry cleaning and industry washing for many times, the application adapts to the core requirements of wearable scenes such as reflective clothing, and the reflective cloth has both safety warning function (stable retroreflection performance) and durability (frequent washing and deformation resistance), and the application value of the reflective material in the movable protection field is expanded.
Preferably, the application of the composite adhesive for the reflective cloth material comprises the steps of mixing the composite adhesive with a crosslinking system and silver paste to obtain a mixed solution, coating the mixed solution on a bead planting film, drying, and then compounding the bead planting film with a cloth base, wherein the cloth base is chemical fiber cloth or TC cloth, the crosslinking system comprises, by mass, 4-8 parts of isocyanate crosslinking agent, 0.1-0.5 part of epoxy crosslinking agent, 0.4-0.6 part of silane coupling agent and 0.65-0.85 part of silver paste when 100 parts of the composite adhesive are used.
The compound glue and the crosslinking system and the silver paste can be mixed to realize the multicomponent synergistic effect. The terminal carboxyl of the composite adhesive provides active sites for the crosslinking reaction and reacts with a crosslinking system to form a more stable three-dimensional network structure, the silver paste is uniformly dispersed in the mixed solution, so that the retroreflection performance of the reflective cloth can be enhanced, the uniform dispersion of all components is ensured in the mixing process, and the local performance deviation is avoided.
The glass beads on the surface of the bead implantation film are of a core structure for realizing retroreflection by the aid of reflective cloth, after the mixed solution is coated on the bead implantation film, the composite adhesive can be firmly combined with the surface of the glass beads through carboxyl groups (modified by a silane coupling agent), the solvent can be removed in a drying step to form a stable adhesive layer by the composite adhesive, shrinkage or bubbles of the adhesive layer caused by solvent residues are avoided (tight combination of the adhesive layer and the bead implantation film is guaranteed), the composite adhesive is compounded with a cloth base after being dried, and base fibers can be fully infiltrated by the aid of proper viscosity (permeability under high solid content) of the composite adhesive to form an integrated structure of the bead implantation film, the adhesive layer and the cloth base, and interlayer delamination is structurally avoided.
Chemical fiber fabrics (chemical fiber fabrics) and TC fabrics (polyester cotton blended fabrics) are common base materials for reflective fabrics, and the suitability of the fiber structure and the composite glue is excellent. The polar groups of the chemical fiber cloth can form intermolecular force with carboxyl of the composite adhesive, cotton fiber gaps of the TC cloth provide channels for the penetration of the composite adhesive, the two can be tightly combined with the composite adhesive, the mechanical properties (such as stretch resistance and bending resistance) of the two cloth bases are matched with the flexibility of the composite adhesive, the stress concentration at the folding position caused by the deformation difference of the base material and the adhesive layer after the compounding can be avoided, and the problem that the folding position of the traditional adhesive is easy to wear is solved.
The three cross-linking agents are in cooperation with each other, so that the performance of the composite adhesive is comprehensively improved. The isocyanate cross-linking agent reacts with active groups of the polyurethane matrix to enhance cohesive strength of the adhesive layer, the epoxy cross-linking agent reacts with terminal carboxyl groups of the composite adhesive to further improve cross-linking density, the silane coupling agent is used as a bridge, one end of the silane coupling agent reacts with surfaces of the glass beads, and the other end of the silane coupling agent forms a covalent bond with the carboxyl groups of the composite adhesive to enhance combination of the adhesive layer and the bead implantation film.
The quality part ratio of each component realizes the performance balance through accurate regulation and control, and the high light reflectivity, the strong binding fastness and the repeated washing resistance of the reflective cloth are realized through synergistic effect.
Preferably, the isocyanate cross-linking agent is L-75 isocyanate cross-linking agent, the epoxy cross-linking agent is GA-240 epoxy cross-linking agent, and the silane coupling agent is KH-560 silane coupling agent.
L-75 (which may be an L-75 isocyanate crosslinker from Bayer, germany) has excellent suitability for reactivity with the composite glue according to the invention. GA-240 (which may be GA-240 epoxy cross-linking agent manufactured by Henschel Co.) has high reactivity of polyfunctional structure and carboxyl at terminal position in the composite gel. KH-560 (which can be KH-560 silane coupling agent produced by the American Dow chemical) has molecular structure containing epoxy group and siloxane group, which is highly matched with the combination requirement of the composite adhesive and the bead planting film (containing glass beads).
Detailed Description
The invention is described in further detail below in connection with the following detailed description, but they are not limiting of the invention:
A composite adhesive for reflecting cloth material is composed of polyurethane matrix containing carboxylic acid as hydroxy acid or binary acid for introducing terminal carboxyl in polyurethane molecular chain.
Preferably, the polyurethane matrix is prepared by polymerizing polyester polyol, diisocyanate, a chain extender, a carboxylic acid monomer, a catalyst, an antioxidant and a solvent in a mass ratio of 36-42:5-7:1-3:1-2:0.12-0.14:0.01-0.02:43-57.
Preferably, the polyester polyol is a mixture of PEA, PDA, PNBA with a mass ratio of 3.5-4.5:0.5-1.5:0.5-1.5 and a molecular weight of 2000, the diisocyanate is a mixture of TDI-80, HDI and MDI-50 with a mass ratio of 2.5-3.5:1:1, the chain extender is a mixture of BDO and DEG with a mass ratio of 1.5-2.5:1, the carboxylic acid monomer is one of anhydrous oxalic acid, malonic acid, 1, 4-succinic acid and 1, 6-adipic acid, the catalyst is a mixture of organic bismuth and TEDA with a mass ratio of 1:1, and the solvent is a mixture of butanone, ethyl acetate and cyclohexane with a mass ratio of 25-30:14-19:4-8.
The preparation method of the composite adhesive for the reflective cloth material comprises the following steps:
S1, solvent dehydration, namely adding a calcium oxide dehydrator into a solvent to remove water, then separating the solvent from the calcium oxide dehydrator, and sealing and preserving the solvent;
s2, dewatering polyester polyol, namely adding the polyester polyol into a reaction kettle, heating to 105-115 ℃, dewatering for 1h under negative pressure, and sealing and cooling to 65 ℃;
s3, preparing a solution, namely dissolving part of diisocyanate in part of solvent to obtain a solution A, and dissolving a chain extender in part of solvent to obtain a solution B;
s4, in the first stage of polymerization, adding an antioxidant, residual diisocyanate and part of solvent into a reaction kettle, reacting for 30min at 65-80 ℃, then dropwise adding the solution A for 30-90 min, keeping the previous temperature, adding part of catalyst and part of solvent, and reacting for 120min at the temperature;
s5, a second stage of polymerization, namely adding carboxylic acid monomers into a reaction kettle, flushing with partial solvent, reacting for 10min at 65-80 ℃, then dropwise adding solution B for 30-60 min, maintaining the previous temperature, adding the rest catalyst and partial solvent, and reacting for 210min under heat preservation;
And S6, adjusting and discharging, namely cooling to 40 ℃, adding the residual solvent, and uniformly stirring to obtain the composite adhesive solution.
Preferably, in the step S3, the solution A consists of 4-5 parts of diisocyanate, 3.5-4.8 parts of butanone and 2-3.5 parts of cyclohexane, and the solution B consists of 1-3 parts of chain extender, 1.5-2.2 parts of butanone and 4-7 parts of ethyl acetate.
Preferably, in the step S4, 1-2 parts of residual diisocyanate, 0.01-0.02 part of antioxidant, 1.2-2.5 parts of cyclohexane as a partial solvent, 0.04-0.05 part of catalyst and 0.8-2 parts of cyclohexane as a partial solvent are added.
Preferably, in the step S5, 2-3 parts of butanone is used as part of solvent for flushing, 0.08-0.09 parts of residual catalyst is added, 0.1-0.5 parts of butanone is used as part of solvent, and in the step S6, 17.9-19.5 parts of butanone and 10-12 parts of ethyl acetate are added.
An application of the composite adhesive for the reflective cloth material, which is an application of the composite adhesive and the cloth base.
The method comprises the steps of mixing a composite adhesive with a crosslinking system and silver paste to obtain a mixed solution, coating the mixed solution on a bead planting film, drying, and then compounding with a cloth base, wherein the cloth base is chemical fiber cloth or TC cloth, the crosslinking system comprises, by mass, 4-8 parts of isocyanate crosslinking agent, 0.1-0.5 part of epoxy crosslinking agent, 0.4-0.6 part of silane coupling agent and 0.65-0.85 part of silver paste when 100 parts of the composite adhesive are obtained.
Preferably, the isocyanate crosslinking agent is an L-75 isocyanate crosslinking agent, the epoxy crosslinking agent is a GA-240 epoxy crosslinking agent, and the silane coupling agent is a KH-560 silane coupling agent.
The polyurethane matrix comprises, by mass, 36, 38, 39, 40, 40.2, 42 parts of polyester polyol, 5, 6, 6.6, 6.8, 7 parts of diisocyanate, 1, 1.9, 2, 3 parts of chain extender, 0.4, 0.8, 1, 1.2, 1.5, 2 parts of carboxylic acid monomer, 0.12, 0.129, 0.13, 0.14 parts of catalyst, 0.01, 0.015, 0.02 parts of antioxidant, and 43, 48.2, 50, 51.8, 57 parts of solvent.
The mass ratio of PEA in the polyester polyol can be 3.5, 4 and 4.5, PDA can be 0.5, 1 and 1.5, and PNBA can be 0.5, 1 and 1.5. The mass ratio of TDI-80 in diisocyanate is 2.5, 3 and 3.5. The mass ratio of BDO in the chain extender can be 1.5, 2 and 2.5. The solvent comprises 25, 27.5 and 30 parts by mass of butanone, 14, 16.5 and 19 parts by mass of ethyl acetate and 4, 6 and 8 parts by mass of cyclohexane.
In the preparation method, in the step S2, the temperature of the reaction kettle is raised to 105-115 ℃, and the reaction kettle can be 105 ℃, 110 ℃ or 115 ℃. And S4, reacting for 30min at 65-80 ℃, wherein the reaction time can be specifically 65-70-72.5-75-80 ℃. And S5, reacting for 10min at 65-80 ℃, wherein the reaction time can be specifically 65 ℃, 70 ℃, 72.5 ℃, 75 ℃ and 80 ℃. In the step S3, the mass ratio of the solution A is specifically 4, 4.5, 5 parts of diisocyanate, 3.5, 4.15, 4.8 parts of butanone, 2, 2.75, 3.5 parts of cyclohexane, and the mass ratio of the solution B is specifically 1,2,3 parts of chain extender, 1.5, 1.85, 2.2 parts of butanone, 4, 5.5, 7 parts of ethyl acetate. The specific mass ratio of the step S4 is that 1, 1.5 and 2 parts of residual diisocyanate are added firstly, 0.01, 0.015 and 0.02 parts of antioxidant, 1.2, 1.85 and 2.5 parts of cyclohexane are used as partial solvents, and 0.04, 0.045 and 0.05 parts of catalyst and 0.8, 1.4 and 2 parts of cyclohexane are used as partial solvents. The specific mass ratio of the step S5 can be that 2, 2.5 and 3 parts of butanone are used as part of solvent for flushing, 0.08, 0.085 and 0.09 parts of residual catalyst are added, 0.1, 0.3 and 0.5 parts of butanone are used as part of solvent, and 17.9, 18.7 and 19.5 parts of butanone and 10, 11 and 12 parts of ethyl acetate are added in the step S6.
In the application, when 100 parts of the composite adhesive are used, the specific parts by mass of the composite adhesive can be 4,5,6,7 and 8 parts of isocyanate crosslinking agents, 0.05, 0.1, 0.15, 0.3 and 0.5 parts of epoxy crosslinking agents, 0.4, 0.5 and 0.6 parts of silane coupling agents and 0.65, 0.75 and 0.85 parts of silver paste.
The isocyanate crosslinking agent may be L-75 isocyanate crosslinking agent of Bayer company, germany, the epoxy crosslinking agent may be GA-240 epoxy crosslinking agent of Henschel company, and the silane coupling agent may be KH-560 silane coupling agent of Dow chemical.
The following samples were set up:
100 parts of a composite glue solution (39.8 parts of polyester polyol, 6.5 parts of diisocyanate, 1.5 parts of chain extender 2,1, 4-succinic acid, 0.129 part of catalyst, 0.015 part of antioxidant and 50 parts of solvent), 6 parts of isocyanate crosslinking agent, 0.3 part of epoxy crosslinking agent, 0.75 part of silver paste and 0.5 part of silane coupling agent are taken, and the mixture solution B is obtained after stirring and dispersing uniformly. And coating the mixed solution B on a bead planting film, and respectively compounding the bead planting film with chemical fiber cloth and TC cloth after drying to obtain a reflective cloth sample 1 and a reflective cloth sample 2.
100 Parts of a composite glue solution (39.8 parts of polyester polyol, 6.5 parts of diisocyanate, 1.5 parts of chain extender 2,1, 6-adipic acid, 0.129 part of catalyst, 0.015 part of antioxidant and 50 parts of solvent), 6 parts of isocyanate crosslinking agent, 0.3 part of epoxy crosslinking agent, 0.75 part of silver paste and 0.5 part of silane coupling agent are taken, and the mixed solution C is obtained after stirring and dispersing uniformly. And coating the mixed solution C on a bead planting film, and respectively compounding the bead planting film with chemical fiber cloth and TC cloth after drying to obtain a reflective cloth sample 3 and a reflective cloth sample 4.
The comparative example selects the prior Hangao LOCTITE S3116 glue, and the solid content of the glue is diluted by ethyl acetate to be consistent with the compound glue solution (polyester polyol 39.8, diisocyanate 6.5, chain extender 2,1, 4-succinic acid 1.5, catalyst 0.129, antioxidant 0.015 and solvent 50). 100 parts of the comparative composite glue solution, 6 parts of isocyanate crosslinking agent, 0.3 part of epoxy crosslinking agent, 0.75 part of silver paste and 0.5 part of silane coupling agent are taken, and the mixed solution D is obtained after stirring and dispersing uniformly. The mixed solution D was coated on a bead-planting film, and after drying, it was compounded with a chemical fiber cloth and a TC cloth, respectively, to obtain a reflective cloth comparative example 1 and comparative example 2.
Samples 1-4 and comparative examples 1-2 were taken and the following comparative tests were performed:
And (3) a family water washing test, namely according to the family washing and drying program for the textile test of GB/T8629-2017, the used washing machine type is an A-type standard washing machine, namely a horizontal roller and front door feeding type, the dryer type is an A1-type overturning dryer, namely a ventilation type, and the washing program number is 9N h. The water temperature is 60 ℃, and the detergent is a common household detergent. The washing and drying times are 50 times.
Dry cleaning test according to the second part of professional maintenance dry cleaning and wet cleaning of fabrics and garments of GB/T19981.2-2014, the used washing machine is a reversible, roller type and totally-enclosed commercial dry cleaning machine using tetrachloroethylene as a solvent, the washing agent is tetrachloroethylene, the dry cleaning procedure is a dry cleaning procedure conforming to the standard, and the drying mode is natural drying. The number of dry cleaning was 25.
Industrial washing test according to ISO 15797-2002 textile-working clothes test industrial washing and finishing procedure, the used washing machine is a drum washing machine conforming to the standard, the dryer is a ventilated turnover dryer conforming to the standard, the washing agent is a washing agent conforming to the industrial washing standard, and the washing procedure is a washing procedure standardized by the corresponding washing agent. The washing and drying times are 50 times.
And (3) testing the retroreflection coefficient, namely, using special testing equipment according to the coplanar geometric method of the JT/T689-2007 retroreflection coefficient testing method, wherein the incident angle is 0.2 degrees, and the observation angle is-4 degrees.
Test results:
Results of 50 home water washes:
| Retroreflective coefficient before washing | Retroreflective coefficient after washing | Attenuation Rate | Surface condition after washing | Folding position after washing | |
| Sample 1 | 598 | 326 | 45.48% | Smooth surface | Substantially free of abrasion |
| Sample 2 | 596 | 317 | 46.81% | Smooth surface | Substantially free of abrasion |
| Sample 3 | 577 | 366 | 36.57% | Smooth surface | Substantially free of abrasion |
| Sample 4 | 579 | 343 | 40.76% | Smooth surface | Substantially free of abrasion |
| Comparative example 1 | 595 | 243 | 59.16% | The surface is slightly rough | Part of the wear of the aluminized layer |
| Comparative example 2 | 580 | 251 | 56.72% | The surface is slightly rough | Part of the wear of the aluminized layer |
Dry cleaning 25 times:
| retroreflective coefficients before dry cleaning | Retroreflective coefficients after dry cleaning | Attenuation Rate | Surface condition after dry cleaning | Folding situation after dry cleaning | |
| Sample 1 | 599 | 416 | 30.55% | Smooth surface | Substantially free of abrasion |
| Sample 2 | 597 | 408 | 31.66% | Smooth surface | Substantially free of abrasion |
| Sample 3 | 580 | 425 | 26.72% | Smooth surface | Substantially free of abrasion |
| Sample 4 | 578 | 422 | 26.99% | Smooth surface | Substantially free of abrasion |
| Comparative example 1 | 589 | 351 | 40.41% | Smooth surface | Complete wear |
| Comparative example 2 | 587 | 344 | 41.40% | Smooth surface | Complete wear |
Industrial wash 50 results:
| Industrial pre-wash retroreflectivity | Retroreflective coefficients after industrial washing | Attenuation Rate | Industrial post-wash surface conditions | Folding position after industrial washing | |
| Sample 1 | 597 | 276 | 53.77% | Smooth surface | Slight abrasion of aluminized layer |
| Sample 2 | 598 | 268 | 55.18% | Smooth surface | Slight abrasion of aluminized layer |
| Sample 3 | 581 | 285 | 50.95% | Smooth surface | Slight abrasion of aluminized layer |
| Sample 4 | 580 | 282 | 51.38% | Smooth surface | Slight abrasion of aluminized layer |
| Comparative example 1 | 591 | 183 | 69.04% | The surface is slightly rough | Complete wear |
| Comparative example 2 | 590 | 170 | 71.19% | The surface is slightly rough | Complete wear |
The analysis results show that the washing fastness of samples 1-4 is better than that of the existing comparative examples 1-2. According to the invention, after the carboxyl is introduced by the dibasic acid or the hydroxy acid, the carboxylic acid group can react with the aluminized layer to form an ionic bond, so that the aluminized layer and the composite adhesive are better combined, meanwhile, the carboxylic acid group can also form a covalent bond with the silane coupling agent with epoxy groups, so that the composite adhesive can be better bonded through the silane coupling agent and the glass beads and is not easy to fall off in the washing process, the four-functional epoxy curing agent is added to react with the carboxyl, so that the crosslinking density can be improved, and meanwhile, the consumption of the isocyanate curing agent can be reduced, so that the cohesive strength and solvent resistance can be effectively improved on the premise that the flexibility is ensured.
In summary, the foregoing description is only of the preferred embodiments of the present invention, and all equivalent changes and modifications that come within the scope of the present invention are desired to be covered thereby.
Claims (10)
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| CN103157493A (en) * | 2013-03-21 | 2013-06-19 | 北京化工大学 | Noble metal supported composite functional nano sphere catalyst having recoverability function and application thereof in catalyzing reduction of p-nitrophenol |
| CN103157493B (en) * | 2013-03-21 | 2015-01-28 | 北京化工大学 | Noble metal supported composite functional nano sphere catalyst having recoverability function and application thereof in catalyzing reduction of p-nitrophenol |
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