CN103965816A - A kind of emulsion adhesive for low-VOC high-performance non-woven fabric material and preparation method thereof - Google Patents

Abstract

The invention discloses an emulsion adhesive for a low-VOC high-performance non-woven fabric material and a preparation method thereof. The emulsion adhesive is prepared by a semi-continuous core-shell polymerization method. By reasonably selecting reaction monomers and reaction processes, particularly using the cationic surfactant to modify the montmorillonite, the emulsion adhesive not only can obtain excellent adhesion, bonding and anchoring effects on non-woven fabric materials, but also has low VOC, no pollution, environmental protection, can replace a plurality of related imported products in the current market, and has wide and good application prospect.

Description

A kind of emulsion adhesive for low-VOC high-performance non-woven fabric material and preparation method thereof

【Technical field】

The invention relates to an emulsion adhesive and a preparation method thereof, in particular to an emulsion adhesive for low-VOC high-performance non-woven fabric materials and a preparation method thereof, belonging to the technical field of adhesives.

【Background technique】

Non-woven fabrics (also known as "non-woven fabrics") are widely used in industrial filtration, construction engineering, medical materials, and other fields, and the scope of application is expanding rapidly. In recent decades, my country's non-woven fabric technology has developed rapidly. In 2010, the output of non-woven fabric materials has reached 2.6 million tons, accounting for about 30% of the global total output, and the output ranks first in the world. However, at present, my country's non-woven fabric-related technologies are relatively backward, especially because the technological development of chemically bonded non-woven fabrics is very backward, resulting in a relatively low output of high-performance non-woven fabric materials in my country and is greatly constrained by others. At present, the adhesives used for non-woven fabrics are mainly synthetic resin emulsion adhesives, and their varieties generally include polyvinyl acetate, polyacrylate, polyacrylonitrile synthetic rubber emulsion, etc. The emulsion adhesive uses water as the dispersion medium, which has less pollution, less pollution to the environment, and the production cost is relatively low, and the production equipment is relatively simple. At present, related products imported from abroad are mainly used in China, which requires a large amount of foreign exchange, and many domestic manufacturers cannot bear it.

The emulsion adhesive used for bonding non-woven fabrics is one of the technical bottlenecks currently restricting the development of my country's non-woven fabric industry. Although many manufacturers in my country can produce corresponding products, from the perspective of technical content, the emulsion adhesives for non-woven fabrics are still in the initial stage in China, and the application performance of the products such as bonding is poor and cannot meet the higher requirements. . At the same time, with the improvement and promotion of environmental protection laws and regulations at home and abroad, many fields have higher and higher requirements for the safety and environmental protection performance of non-woven adhesives, and strictly require the toxicity of emulsion adhesives to be controlled at a minimum. However, the latex adhesives for bonding non-woven fabrics currently produced in China contain relatively toxic substances such as formaldehyde and phenol, and are easy to release carcinogens such as formaldehyde during processing and use, which is very inconsistent with today's green environmental protection demands.

Therefore, in order to promote the rapid development of my country's non-woven fabric related industries, expand the development of my country's non-woven fabric industry and improve the competitiveness of non-woven fabric products, and reduce the gap between my country's non-woven fabric emulsion adhesives and foreign products, my country urgently needs to develop application performance Excellent and environmentally friendly special adhesive for non-woven fabrics.

【Content of invention】

The purpose of the present invention is to overcome the defects of the above-mentioned prior art and products, and provide a non-woven material with excellent adhesion, bonding, fixation and reinforcement effects, and the corresponding coating film has excellent strength, water resistance and flexibility. Low-VOC high-performance emulsion adhesive for non-woven materials, suitable for non-woven materials such as non-woven fibers.

Another object of the present invention is to provide a method for preparing the above-mentioned emulsion adhesive.

In order to achieve the above object, the present invention adopts the following technical scheme: acrylate monomers such as styrene, methyl methacrylate, and butyl acrylate are used as main polymerization monomers, and functional monomers containing carboxyl and hydroxyl groups are used as modified monomers. , to prepare emulsion adhesives for non-woven materials by semi-continuous core-shell polymerization. The specific technical scheme is as follows:

A low-VOC high-performance non-woven fabric material emulsion adhesive is characterized in that it consists of the following components by weight:

In the present invention, the hard monomer is one of styrene, methyl methacrylate, ethyl methacrylate, diallyl phthalate, diallyl isophthalate and glycidyl methacrylate species or any combination thereof.

The soft monomer in the present invention is one of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate or any combination thereof.

The functional monomers in the present invention are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylic acid and methacrylic acid one or any combination of them. Functional monomers mainly provide sufficient hydroxyl or carboxyl groups to improve the adhesion and bonding of the emulsion adhesive.

The initiator in the present invention is one of ammonium persulfate, potassium persulfate, sodium persulfate, tert-butyl hydroperoxide and azodiisopropylimidazoline hydrochloride or any combination thereof.

The emulsifier in the present invention is sodium lauryl sulfate, sodium dodecylbenzenesulfonate, AES, AEO-9, OP-10, Tween-60, Tween-80, Span-20, Span-60 and Span One of -80 or any combination thereof. Emulsifiers can greatly reduce the interfacial tension, so that the immiscible oil-water two-phase can be transformed into a stable existence by stirring, and it is an essential component of emulsion polymerization.

The pH regulator in the present invention is one of 2-amino-2-methyl-1-propanol (AMP-95), KOH, NaOH, ammonia water, sodium bicarbonate or any combination thereof. The main function of the pH regulator is to adjust the emulsion to a weakly alkaline state, and the ammonia water can be adjusted to a concentration of 1wt%, 5wt%, and 10wt%, which is convenient for use.

The modified montmorillonite in the present invention is prepared by the following preparation method:

The cationic surfactant is completely dissolved in deionized water to obtain a solution with a solid content of 10 to 15% by weight; then according to the mass ratio of m (montmorillonite): m (cation surfactant) = 10: 1 to 10: 3 Slowly add montmorillonite into the obtained solution, stir until it is completely dispersed, heat up to 60-80°C and keep it warm for 10-25 minutes, and finally filter and dry to obtain modified montmorillonite;

The cationic surfactant is one or more of cetyltrimethylammonium chloride, cetyltrimethylammonium bromide and cetyldimethylbenzylammonium chloride.

Under normal circumstances, the adhesion of emulsion adhesives on the textile substrate is poor, and it is easy to fall off from the surface of the textile under the action of environmental factors or external forces. This is the most difficult problem in this field at present. Recent studies have shown that the addition of cationic surfactants can effectively fix the adhesion of emulsion adhesive coatings to woven fabrics. However, the emulsion adhesive system mainly uses anionic surfactants, and the added cationic surfactants will immediately react with them and become invalid, which will quickly cause destructive consequences such as flocculation, sedimentation, and demulsification of the emulsion system.

To overcome this deficiency, the present invention creatively uses cationic surfactants to modify montmorillonite. Montmorillonite is a layered silicate, and the interlayer contains a certain amount of inorganic cations such as Na ⁺ or Li ⁺ . When contacting cationic surfactants, organic cations are easy to replace the interlayer inorganic cations. The organic cations that have entered the interlayer of the montmorillonite are no longer in contact with the anionic surfactant in the emulsion system due to the blocking and shielding effect of the layered structure, so the emulsion system is very stable. After the film is formed, the organic cations will gradually permeate out to promote the adhesion and adhesion between the coating and the woven substrate.

A method for preparing the above-mentioned emulsion adhesive for low-VOC high-performance non-woven fabric materials is characterized in that it is prepared by a semi-continuous core-shell polymerization method.

The present invention prepares the emulsion adhesive by the semi-continuous core-shell polymerization method and comprises the following specific steps:

(1) First fully dissolve the emulsifier and modified montmorillonite in deionized water, then add 1/4~1/2 hard monomer, 1/4~1/2 soft monomer, 1/5~1 /3 functional monomer, fully stir to form a pre-reaction liquid, then take out 1/3-1/2 of the pre-reaction liquid in the reaction equipment, add 1/2 initiator, and raise the temperature to 80-85 ° C, keep warm for 20 ~60min to react, meanwhile, the rest of the pre-reaction solution is still kept stirring;

(2) Then cool down the reaction system in the reaction equipment to 35-45°C, add the remainder of the pre-reaction solution and the remainder of the initiator, then raise the temperature to 80-85°C, and keep it warm for 1-4 hours;

(3) Then add the remaining amount of hard monomer, the remaining amount of soft monomer and the remaining amount of functional monomer, keep it warm at 80-85°C for 1-3 hours, and finally lower it to room temperature and add a pH regulator to adjust the pH to 9-10. Let stand for 5-20 minutes and discharge.

Compared with the prior art, the present invention has the following advantages:

(1) The present invention, through the rational selection of the reaction monomer and the reaction process, especially the use of cationic surfactant modified montmorillonite, makes the emulsion adhesive not only obtain excellent adhesion, bonding, Anchoring effect, low VOC, no pollution, green and environmental protection, can replace many related imported products on the market, and has broad and good application prospects.

(2) The present invention adopts a semi-continuous core-shell polymerization method, which has a simple preparation process, is easy to control the polymerization system, and has low cost. The emulsion polymerization method of the invention uses water as the dispersion medium, is cheap and safe, avoids the trouble of using expensive organic solvents and recovering solvents, and reduces the possibility of causing fire and polluting the environment.

【Detailed ways】

The present invention will be further described below in conjunction with the examples. It should be noted that the examples are not intended to limit the protection scope of the present invention.

Example 1:

Preparation of modified montmorillonite:

Completely dissolve the cationic surfactant in deionized water to obtain a solution with a solid content of 12wt%; then slowly add the montmorillonite according to the mass ratio of m(montmorillonite):m(cationic surfactant)=10:2 In the solution, stir until it is completely dispersed, raise the temperature to 75°C and keep it warm for 20 minutes, and finally filter and dry to obtain the modified montmorillonite.

A kind of low-VOC high-performance non-woven fabric material uses the weight grouping of emulsion adhesive as follows:

The preparation technology of embodiment 1:

(1) First, fully dissolve emulsifier AES and modified montmorillonite in deionized water, then add 1/3 hard monomer styrene and diallyl isophthalate, 1/3 soft monomer butyl acrylate ester, 1/4 functional monomer 2-hydroxyethyl methacrylate and acrylic acid, fully stirred to form a pre-reaction liquid, then take out 1/3~1/2 of the pre-reaction liquid in the reaction equipment, add 1/ 2 Initiator potassium persulfate, and heat up to 80-85°C, keep warm for 30 minutes to react, and at the same time, keep the remaining pre-reaction solution still in a stirring state;

(2) Then the reaction system in the reaction equipment is cooled to 40°C, the remaining amount of pre-reaction solution and the remaining amount of initiator potassium persulfate are added, and then the temperature is raised to 80-85°C, and the temperature is kept for 3h;

(3) Add the remaining amount of hard monomer, the remaining amount of soft monomer and the remaining amount of functional monomer, keep it warm at 80-85°C for 2 hours, and finally lower it to room temperature and adjust the pH value to 9-10 with 1wt% dilute ammonia water. Let stand for 5-20 minutes and discharge.

Example 2:

Preparation of modified montmorillonite:

Completely dissolve the cationic surfactant in deionized water to obtain a solution with a solid content of 13wt%; then slowly add the montmorillonite according to the mass ratio of m(montmorillonite):m(cationic surfactant)=10:2 In the solution, stir until it is completely dispersed, raise the temperature to 70°C and keep it warm for 15 minutes, and finally filter and dry to obtain the modified montmorillonite.

A kind of low-VOC high-performance non-woven fabric material uses the weight component of emulsion adhesive as follows:

The preparation technology of embodiment 2:

(1) First, fully dissolve the emulsifier OP-10 and modified montmorillonite in deionized water, then add 1/3 of the hard monomer styrene and methyl methacrylate, and 1/3 of the soft monomer butyl acrylate , 1/4 functional monomer -2-hydroxyethyl methacrylate, fully stirred to form a pre-reaction liquid, then take out 1/3~1/2 of the pre-reaction liquid in the reaction equipment, add 1/2 initiator ammonium persulfate, and raised to 80-85°C, kept warm for 30 minutes, and at the same time, kept the remainder of the pre-reaction solution still in a stirring state;

(2) Then cool down the reaction system to 40°C, add the rest of the pre-reaction solution and the rest of the initiator ammonium persulfate, then raise the temperature to 80-85°C, and keep it warm for 3h;

(3) Then add the remaining amount of hard monomer, remaining amount of soft monomer and remaining amount of functional monomer, keep it warm at 80-85°C for 2 hours, and finally cool down to room temperature and add AMP-95 to adjust the pH value to 9-10, statically Set it aside for 5-20 minutes and then discharge.

Example 3:

Preparation of modified montmorillonite:

Completely dissolve the cationic surfactant in deionized water to obtain a solution with a solid content of 10wt%; then slowly add the montmorillonite according to the mass ratio of m(montmorillonite):m(cationic surfactant)=10:1 In the solution, stir until it is completely dispersed, raise the temperature to 60°C and keep it warm for 10 minutes, and finally filter and dry to obtain the modified montmorillonite.

A kind of low-VOC high-performance non-woven fabric material uses the weight component of emulsion adhesive as follows:

The preparation technology of embodiment 3:

(1) First, fully dissolve emulsifier OP-10 and modified montmorillonite in deionized water, then add 1/3 hard monomer styrene, 1/3 soft monomer butyl acrylate, 1/4 functional Monomer 2-hydroxyethyl methacrylate, fully stirred to form a pre-reaction liquid, then take out 1/3~1/2 of the pre-reaction liquid in the reaction equipment, add 1/2 initiator ammonium persulfate, and raise the temperature To 80 ~ 85 ℃, keep warm for 30 minutes, at the same time, keep the rest of the pre-reaction solution still in a stirring state;

(2) Then cool down the reaction system to 40°C, add the rest of the pre-reaction solution and 1/2 initiator ammonium persulfate, then raise the temperature to 80-85°C, and keep it warm for 3h;

(3) Then add the remaining amount of hard monomer, remaining amount of soft monomer and remaining amount of functional monomer, keep it warm at 80-85°C for 2 hours, and finally cool down to room temperature and add AMP-95 to adjust the pH value to 9-10, statically Set it aside for 5-20 minutes and then discharge.

Example 4:

Preparation of modified montmorillonite:

Completely dissolve the cationic surfactant in deionized water to obtain a solution with a solid content of 15wt%; then slowly add the montmorillonite according to the mass ratio of m(montmorillonite):m(cationic surfactant)=10:3 In the solution, stir until it is completely dispersed, raise the temperature to 80°C and keep it warm for 25 minutes, and finally filter and dry to obtain the modified montmorillonite.

A kind of low-VOC high-performance non-woven fabric material uses the weight component of emulsion adhesive as follows:

The preparation technology of embodiment 4:

(1) First, fully dissolve emulsifier AES and modified montmorillonite in deionized water, then add 1/3 hard monomer styrene, 1/3 soft monomer butyl acrylate, and 1/4 functional monomer For methacrylic acid, stir well to form a pre-reaction solution, then put 1/3~1/2 of the pre-reaction solution in the reaction equipment, add 1/2 initiator ammonium persulfate, and raise the temperature to 80~85°C, keep warm 40min, meanwhile, keep the rest of the pre-reaction solution still in stirring state;

(2) Then cool down the reaction system to 40°C, add the rest of the pre-reaction solution and 1/2 initiator ammonium persulfate, then raise the temperature to 80-85°C, and keep it warm for 3h;

(3) Then add the remaining amount of hard monomer, the remaining amount of soft monomer and the remaining amount of functional monomer, keep it warm at 80-85°C for 2 hours, and finally lower it to room temperature, add AMP-95 to adjust the pH value to 9-10, and let it stand After 5 to 20 minutes, the material can be discharged.

Example 5:

Preparation of modified montmorillonite:

Completely dissolve the cationic surfactant in deionized water to obtain a solution with a solid content of 15wt%; then slowly add the montmorillonite according to the mass ratio of m(montmorillonite):m(cationic surfactant)=10:3 In the solution, stir until it is completely dispersed, raise the temperature to 80°C and keep it warm for 25 minutes, and finally filter and dry to obtain the modified montmorillonite.

A kind of low-VOC high-performance non-woven fabric material uses the weight component of emulsion adhesive as follows:

The preparation technology of embodiment 5:

(1) First, fully dissolve the emulsifier and modified montmorillonite in deionized water, then add 1/2 hard monomer, 1/2 soft monomer, and 1/3 functional monomer, and stir well to form a pre- reaction solution, then put 1/3~1/2 of the pre-reaction solution in the reaction equipment, add 1/2 initiator, and raise the temperature to 80-85°C, keep it warm for 60 minutes, and at the same time, keep the rest of the pre-reaction solution still at Stirring state;

(2) Then cool down the reaction system to 45°C, add the rest of the pre-reaction solution and 1/2 initiator, then raise the temperature to 80-85°C, and keep it warm for 4h;

(3) Then add the remaining amount of hard monomer, the remaining amount of soft monomer and the remaining amount of functional monomer, keep it warm at 80-85°C for 3 hours, and finally lower it to room temperature and add a pH regulator to adjust the pH value to 9-10. Set it aside for 5-20 minutes and then discharge.

Embodiment 6:

Preparation of modified montmorillonite:

Completely dissolve the cationic surfactant in deionized water to obtain a solution with a solid content of 10wt%; then slowly add the montmorillonite according to the mass ratio of m(montmorillonite):m(cationic surfactant)=10:1 In the solution, stir until it is completely dispersed, raise the temperature to 60°C and keep it warm for 10 minutes, and finally filter and dry to obtain the modified montmorillonite.

A kind of low-VOC high-performance non-woven fabric material uses the weight component of emulsion adhesive as follows:

The preparation technology of embodiment 6:

(1) First, fully dissolve the emulsifier and modified montmorillonite in deionized water, then add 1/4 of the hard monomer, 1/4 of the soft monomer, and 1/5 of the functional monomer, and stir well to form a pre- reaction solution, then put 1/3~1/2 of the pre-reaction solution in the reaction equipment, add 1/2 initiator, and raise the temperature to 80-85°C, keep it warm for 20min, and keep the rest of the pre-reaction solution still at Stirring state;

(2) Then cool down the reaction system to 35°C, add the rest of the pre-reaction solution and 1/2 initiator, then raise the temperature to 80-85°C, and keep it warm for 1h;

(3) Then add the remaining amount of hard monomer, the remaining amount of soft monomer and the remaining amount of functional monomer, keep it warm at 80-85°C for 1 hour, and finally lower it to room temperature and add a pH regulator to adjust the pH value to 9-10. Set it aside for 5-20 minutes and then discharge.

Examples 1-6 were applied to non-woven fibers and various tests were carried out, and the results are shown in Table 1.

Table 1: Test results of finished emulsion adhesives for non-woven fabrics

It can be seen from Table 1 that the quantitative, thickness, air permeability, bending strength, bursting strength and other performance indicators of the emulsion adhesive for non-woven fabrics of the present invention are better, and it can be applied to non-woven fabrics to obtain good adhesion and fixation. And the enhancement effect, at the same time, there is no release of carcinogens such as formaldehyde and phenol, which not only basically fully meets the relevant use requirements and standards such as non-woven reinforcement treatment, but also is green and environmentally friendly, and will not pollute the environment.

The purpose of the above-mentioned reference examples is to describe the present invention in detail, and it is illustrative rather than limiting. For those skilled in the art, without departing from the scope and general concept of the present invention, it is obvious to make different modifications and changes according to the method of the present invention, and should fall within the protection scope of the present invention.

Claims (10)

1. a low VOC and high performance nonwoven cloth material emulsion adhesive, is characterized in that being made up of following parts by weight of component:

2. a kind of low VOC and high performance nonwoven cloth material emulsion adhesive according to claim 1, is characterized in that described hard monomer is a kind of or its arbitrary combination in vinylbenzene, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, Phthalic acid, diallyl ester, diallyl isophthalate and glycidyl methacrylate.

3. a kind of low VOC and high performance nonwoven cloth material emulsion adhesive according to claim 1, is characterized in that described soft monomer is a kind of or its arbitrary combination in ethyl propenoate, butyl acrylate, ethyl acrylate and lauryl acrylate.

4. a kind of low VOC and high performance nonwoven cloth material emulsion adhesive according to claim 1, is characterized in that described functional monomer is a kind of or its arbitrary combination in 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, vinylformic acid and methacrylic acid.

5. a kind of low VOC and high performance nonwoven cloth material emulsion adhesive according to claim 1, is characterized in that described initiator is a kind of or its arbitrary combination in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, tertbutyl peroxide and azo di-isopropyl imidazoline salt hydrochlorate.

6. a kind of low VOC and high performance nonwoven cloth material emulsion adhesive according to claim 1, is characterized in that described emulsifying agent is a kind of or its arbitrary combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, AES, AEO-9, OP-10, Tween-60, Tween-80, Span-20, Span-60 and Span-80.

7. a kind of low VOC and high performance nonwoven cloth material emulsion adhesive according to claim 1, is characterized in that described pH adjusting agent is a kind of or its arbitrary combination in 2-amino-2-methyl-1-propanol, KOH, NaOH, ammoniacal liquor, sodium bicarbonate.

8. a kind of low VOC and high performance nonwoven cloth material emulsion adhesive according to claim 1, is characterized in that described modified montmorillonite usedly prepare by following preparation method:

Cats product is dissolved in deionized water, obtains the solution that solid content is 10～15wt% completely; Then according to the mass ratio of m (montmorillonite): m (cats product)=10:1～10:3, montmorillonite is slowly added in gained solution, stir until after disperseing completely, be warming up to 60～80 DEG C and insulation reaction 10～25min, finally filter and be dried make modified montmorillonite used.

9. a preparation method for the use of the low VOC and high performance nonwoven cloth material described in any one emulsion adhesive in claim 1-8, is characterized in that making by semicontinuous hud polymerization method.

10. the preparation method of emulsion adhesive for a kind of low VOC and high performance nonwoven cloth material according to claim 9, is characterized in that comprising following concrete steps:

(1) first by emulsifying agent and modified montmorillonite used being dissolved in fully completely in deionized water, add again 1/4～1/2 hard monomer, 1/4～1/2 soft monomer, 1/5～1/3 functional monomer, stir and form pre-reaction liquid, then take out 1/3～1/2 pre-reaction liquid in conversion unit, add 1/2 initiator, and be warming up to 80～85 DEG C, insulation 20～60min reacts, meanwhile, the pre-reaction liquid of surplus still keeps whipped state;

(2) then the reaction system in conversion unit is cooled to 35～45 DEG C, adds pre-reaction liquid and the surplus initiator of surplus, then be warming up to 80～85 DEG C, insulation 1～4h;

(3) add again surplus hard monomer, surplus soft monomer and surplus functional monomer, at 80～85 DEG C, be incubated 1～3h, then being down to room temperature, to add pH adjusting agent to regulate pH value be 9～10, then after standing 5～20min, discharging makes nonwoven cloth material emulsion adhesive.