CN1641098A - Baking-free no-methanal coating dyeing nano adhesive water-based latex - Google Patents

Abstract

The invention relates to a non-baking formaldehyde-free paint dyed nano-adhesive water-based latex, wherein the adhesive is formed by the reaction of the following components: pre-crosslinking monomers, soft monomers, hard monomers, hydrophilic monomers, Compound emulsifier and initiator for anionic and nonionic emulsifiers. It is prepared by adding the mixture of pre-crosslinking monomer, soft monomer, hard monomer and hydrophilic monomer and initiator aqueous solution into emulsifier and distilled water for reaction, neutralization and filtration. The water-based latex not only has a simple preparation method, but also can be used in textile printing and dyeing processing, and only needs to be dried below 100°C without baking. It is a textile paint dyed latex with good shear resistance and stability, not easy to stick to the roll and meets the requirements of continuous production.

Description

Non-baking formaldehyde-free paint dyeing nano-adhesive water-based latex

Technical field:

The utility model relates to the field of light chemical industry, in particular to a non-baking and formaldehyde-free paint dyeing nano-adhesive water-based latex, its preparation method and application, including the preparation of the water-based latex and its dyeing of paint on pure cotton and silk fabrics application.

Background technique:

At present, the components of known textile coating adhesives mostly contain active groups of methylolacrylamides, and the fabrics need to be baked at high temperature in the process of use to obtain ideal dry and wet rubbing fastness. . On the one hand, high temperature baking (usually around 150°C) will damage the physical properties of dyed fabrics. On the other hand, relying on the methylolacrylamide active group to produce crosslinking after high temperature action and the inevitable release of formaldehyde during the taking process, the environment is polluted. Recently, it has also been reported that low-temperature formaldehyde-free printing adhesives can be produced, but they still need to be baked, but the temperature is lower (100-130 ° C), and most of them use epichlorohydrin instead of N-methylolacrylamide. As an active group for post-baking cross-linking. This improved method not only cannot fundamentally solve the unfavorable factors in product performance caused by high temperature treatment, but also has the potential pollution of absorbable organic halogens. In the evaluation of adhesive properties, the softness of the fabric after dyeing is the key to measure. In addition, the dry and wet rubbing fastness must also meet higher requirements. The physical stability of the adhesive latex used for paint dyeing, especially the shear resistance stability of the adhesive latex will directly affect whether the continuous production of paint dyeing can be realized, and the lack of shear resistance means that when using During the process, the adhesive is easy to adhere to the roll used for paint dyeing, resulting in waste and inconvenience in production. The development of adhesive latex that can be applied to pigment dyeing is of special significance to the environmental friendliness of dyeing and printing processes, because theoretically speaking, pigment dyeing and pigment printing processes basically produce no wastewater.

Invention content:

The object of the present invention is to provide a kind of non-baking formaldehyde-free paint dyeing nano-adhesive water-based latex.

The object of the present invention also provides a method for preparing the above-mentioned non-baking and formaldehyde-free paint dyeing nano-adhesive aqueous latex.

Another object of the present invention is to provide an application of the above-mentioned non-baking and formaldehyde-free paint dyeing nano-adhesive aqueous latex.

The non-baking formaldehyde-free paint dyeing nano-adhesive aqueous latex of the present invention is a kind of water-based latex that can be used for non-baking and formaldehyde-free nano-adhesives including real silk fabrics, pure cotton fabric paint dyeing, and paint printing. The main index particle size of latex is less than 300nm, and the average particle size is about 100nm. The water-based latex can be dried at 100 DEG C without baking, has a soft touch, and has dry and wet rubbing fastness meeting requirements. It is not easy to stick to the roll, and the shear resistance stability meets the requirements of continuous production.

The technical scheme of the present invention is: when synthesizing the binder, introduce an appropriate amount of pre-crosslinked functional monomers with longer carbon chains: ethylene glycol dimethacrylate, diethylene glycol dimethyl acrylate Dilute acid ester or triethylene glycol dimethacrylate. Since the cross-link density is not very high, its restriction on molecular motion is limited. When the latex is formed into a film, the motion and interdiffusion of macromolecular segments between the particles can still be carried out effectively, so that the film can still be formed effectively, and the formed adhesive film is flexible and bright. The selected synthetic monomer has a suitable glass transition temperature and does not contain hydroxymethyl acrylic acid amine active groups, so the latex has the problem of environmental pollution of low-temperature film formation at 80-100°C without formaldehyde release. In addition, the dosage of the hydrophilic monomer methacrylic acid in the synthetic monomer is increased within the range permitted by the fastness, thereby improving the shear resistance of the adhesive. Methacrylic acid is a kind of hydrophilic monomer, and its dosage must be controlled within a reasonable range. As the dosage of methacrylic acid increases, the diameter of latex particles becomes smaller and the distribution is even. Shear stability is significantly improved. However, if the amount of hydrophilic monomer is too high, the wet rubbing fastness of printed and dyed fabrics will be reduced. It is necessary to choose a reasonable dosage range.

What the present invention adopts is the synthesis method of pre-crosslinking, and by introducing a certain amount of pre-crosslinking monomer, the adhesive has reached a certain degree of crosslinking during synthesis, thereby improving the performance of the product, and no additional crosslinking agent. The molecular structure simulation diagram of its film-forming structure is shown in Fig. 1 .

The molecular formula can also be simply expressed as follows: mainly it can form a continuous network structure in the adhesive macromolecule:

f is a pre-crosslinked monomer

Among them, M, N, X, Y, S, and n are all natural numbers.

Adhesive among the present invention is generated by following composition reaction:

(1) A pre-crosslinking monomer: ethylene glycol dimethyl acrylate, ethylene glycol dimethyl acrylate or diethylene glycol dimethyl acrylate; or mixed use;

(2) A soft monomer: butyl acrylate, isooctyl acrylate, heptyl acrylate, pentyl acrylate or hexyl acrylate; can be used alone or in combination;

(3) A hard monomer: styrene, methyl methacrylate or acryl cyanide, which can be used alone or in combination;

(4) Hydrophilic monomer methacrylic acid;

(5) An emulsifier is a compound emulsifier of anionic surfactant and nonionic emulsifier, usually the anionic surfactant is sodium lauryl sulfate, and the nonionic emulsifier is TX-30, or the emulsifier with Anion/non-ionic two kinds of surfactant functions or sodium sulfosuccinate with similar structure, combined with Pingpinga O and emulsifier OS to form a compound system, the ratio of anion/non-emulsifier is 1:1-1 : 2; and

(6) Initiator: ammonium persulfate or potassium persulfate.

Among them, the type and amount of pre-crosslinking monomers have an impact on the pre-crosslinking degree and molecular weight of the adhesive, and the pre-crosslinking active monomers with longer molecular chains can significantly improve the physical and mechanical properties of the latex film. , Film brightness, flexibility and elasticity. Types of pre-crosslinking monomers: A: ethylene glycol dimethacrylate; B: ethylene glycol dimethyl acrylate; C: diethylene glycol dimethyl acrylate; A single cross-linking monomer can be used alone, and the various applicable dosages should be within a certain range.

The ratio of the weight of the pre-crosslinking monomer to the total weight W of the soft monomer and the hard monomer is 0.5-6:100. Most preferably: A: 5-6:100; B: 0.8-1.5:100; C: 0.5-1:100.

The so-called 'soft monomer' in the monomer refers to a polymerized monomer with a lower glass transition temperature. In the present invention, a series of monomers such as butyl acrylate, isooctyl acrylate, heptyl acrylate, pentyl acrylate or hexyl acrylate are used. As a soft monomer, the soft monomer component can improve the wettability and adhesion of the latex film to the fabric and pigment particles, and reduce the film-forming temperature.

'Hard monomer' refers to polymerized monomer materials with high and low glass transition temperatures. Styrene, methyl methacrylate or acrylonitrile are used in the present invention. The hard monomer component can improve the mechanical properties of the film, such as abrasion resistance, film strength, etc. The weight ratio of soft and hard monomers is as follows: soft monomer: hard monomer = 2-5:1, 3.5-4:1 is recommended.

Hydrophilic monomer methacrylic acid in the present invention plays a vital role in determining the size of emulsion particles, particle distribution and adhesive latex shear stability, due to the influence of wet rubbing fastness of dyed and printed products Its usage must be controlled within a certain range. The weight ratio of methacrylic acid to W is 2-5:100, preferably 3.5-4:100.

The emulsifier determines the stability of the reaction system, the speed of the reaction and the size of the particles in the emulsion polymerization reaction. A good emulsifier should have an HLB value adapted to the reaction monomer. The emulsifier used in the present invention is an anion/nonionic compound emulsifier. Sodium lauryl sulfate of water chain, non-ionic emulsifier is TX-30, with 30 repeating units of -OCH ₂ CH ₂ , or one with anionic/non-ionic surfactant function or similar structure Sodium sulfosuccinate. It is combined with Pingpingjia O and emulsifier OS to form a compound system. The proportion of emulsifier is as follows:

The weight ratio of yin/non-emulsifier in the main component is 1:1-2.

The compound emulsifier is recommended to be composed of the weight ratio of the following substances: sodium lauryl sulfate 21.70: TX-3032.60: emulsifier OS 9.50: Pingpinga O 36.20.

The weight of emulsifier accounts for 2%-5% of the total weight of the emulsion system, and 3.5% is recommended.

The total weight (W) of soft and hard monomers accounts for 28%-35% of the total weight of the emulsion system, 30% is recommended.

The weight ratio of initiator type and applicable weight to W is: ammonium persulfate or potassium persulfate 0.6-0.9:100, ammonium persulfate is recommended, and the weight ratio to W is 0.7:100.

The preparation method of the non-baking formaldehyde-free paint dyeing nano-adhesive water-based latex of the present invention comprises the following steps:

At 70-90°C, add the initiator into the emulsifier and distilled water, stir evenly, add the mixed monomer of pre-crosslinking monomer, soft monomer, hard monomer and methacrylic acid, react for 0.1-5 hours, and use ammonia water , alkali metal hydroxide or tertiary amine to neutralize and filter. The total weight of the soft monomer and the hard monomer, the weight ratio of the emulsifier to water is 1:0.1～0.2:6～7, recommended 1:0.1～0.15:61:0.1～0.2:6.6～6.8; The total weight of monomer and hard monomer, the weight ratio of pre-crosslinking monomer, methacrylic acid and initiator are 1: 0.004～0.02: 0.025～0.050: 0.004～0.009, the weight ratio of soft monomer and hard monomer It is 75～80:20～25.

Among them, ammonia water, sodium hydroxide or triethylamine are recommended as neutralizers.

The water-based latex of the invention not only has a simple preparation method, but also can be dried at 100 DEG C without baking in the textile printing and dyeing process, has soft hand feeling, and the dry and wet rubbing fastness meet the requirements. It is an auxiliary agent for textile paint dyeing that is not easy to stick to the roll, and its shear resistance stability meets the requirements of continuous production.

Description of drawings

Figure 1: Molecular structure simulation of a non-baking and formaldehyde-free paint dyed nano-adhesive aqueous latex polymer film.

Specific implementation method

The following examples will help to understand the present invention, but do not limit the content of the present invention. In particular the data in the examples do not limit the amount of the individual components used in the invention.

Example 1

The application examples given below can synthesize the adhesive described in this patent, wherein the application effect of the adhesive synthesized according to the formula in Table 1 is listed in Example 8.

Will be equipped with a stirrer, reflux condenser. Place the three-necked flask of the dropping funnel on a constant temperature water bath, add emulsifier and distilled water, stir, heat up to 78-80°C, add initiator, stir for 0.1 hour, add soft/hard monomer, hydrophilic monomer and For the pre-crosslinked monomer monomer, keep warm for 0.5 hours after the dropwise addition, then raise the temperature to about 85°C, keep warm for 1 hour, cool down, neutralize with alkali (ammonia water is recommended), filter, and discharge.

The synthesized adhesive has a particle diameter of about 100nm, is concentrated in distribution, and has excellent shear stability, acid and alkali resistance, electrolyte resistance and dilution resistance.

Table 1: Adhesive composition composition composition ratio Proportion of W Proportion of emulsion system monomer Butyl acrylate 66.70% 100% 30.00% Isooctyl acrylate 13.30% Styrene 15.00% Methyl methacrylate 5.00% Emulsifier Sodium dodecyl sulfate 21.70% 3.50% Emulsifier OS 9.50%

Ping Ping plus O 36.20% TX-30 32.60%  Diethylene glycol dimethacrylate 1.00% Methacrylate 3.50% Ammonium persulfate 0.70% water 66.50%

Example 2

The preparation method is the same as in Example 1.

Table 2: Adhesive composition (the type of pre-crosslinking monomer can be changed, and the amount of emulsifier can be changed) composition composition ratio Proportion of W Proportion of emulsion system monomer Butyl acrylate 66.70% 100% 30.00% Isooctyl acrylate 13.30% Styrene 15.00% Methyl methacrylate 5.00% Emulsifier Sodium dodecyl sulfate 21.70% 3.00% Emulsifier OS 9.50% Ping Ping O 36.20% TX-30 32.60% Ethylene glycol dimethacrylate 5.00% Methacrylate 3.50% Ammonium persulfate 0.70% water 67.00%

Example 3

The preparation method is the same as in Example 1.

Table 3: Adhesive components (different pre-crosslinking monomers can be used in combination) composition composition ratio Proportion of W Proportion of emulsion system

monomer Butyl acrylate 66.70% 100% 30.00%   Isooctyl Acrylate 13.30% Styrene 15.00% Methyl methacrylate 5.00% Emulsifier Sodium dodecyl sulfate 21.70% 3.50% Emulsifier OS 9.50% Ping Ping plus O 36.20% TX-30 32.60% Ethylene glycol dimethacrylate 0.40%  Diethylene glycol dimethacrylate 0.80% Methacrylate 3.50% Ammonium persulfate 0.70% water 66.50%

Example 4

The preparation method is the same as in Example 1.

Table 4: Adhesive composition (type of emulsifier can vary) composition composition ratio Proportion of W Proportion of emulsion system monomer Butyl acrylate 66.70% 100% 30.00% Isooctyl acrylate 13.30% Styrene 15.00% Methyl methacrylate 5.00% Emulsifier Sodium sulfosuccinate 54.00% 3.50% Emulsifier OS 10.50% Ping Ping O 35.50% Diethylene glycol dimethacrylate 1.00% Methacrylate 3.50% Ammonium persulfate 0.70% water 66.50%

Example 5

The preparation method is the same as in Example 1.

Table 5: Adhesive components (initiator types can vary) composition composition ratio Proportion of W Proportion of emulsion system monomer Butyl acrylate 66.70% 100% 30.00% Isooctyl acrylate 13.30% Styrene 15.00% Methyl methacrylate 5.00% Emulsifier Sodium dodecyl sulfate 21.70% 3.50% Emulsifier OS 9.50% Ping Ping O 36.20% TX-30 32.60% Diethylene glycol dimethacrylate 1.00% Methacrylate 3.50% potassium persulfate 0.50% water 66.50%

Example 6

The preparation method is the same as in Example 1.

Table 6: Adhesive composition (the ratio of soft and hard monomers can vary) composition composition ratio Proportion of W Proportion of emulsion system monomer Butyl acrylate 60.00% 100% 30.00% Isooctyl acrylate 15.00% Styrene 18.75% Methyl methacrylate 6.25% Emulsifier Sodium dodecyl sulfate 21.70% 3.50% Emulsifier OS 9.50%

Ping Ping plus O 36.20% TX-30 32.60%  Diethylene glycol dimethacrylate 1.00% Methacrylate 3.50% Ammonium persulfate 0.70% water 66.50%

Example 7

The preparation method is the same as in Example 1.

Table 7: Adhesive constituents (hydrophilic monomers can vary) composition composition ratio Proportion of W Proportion of emulsion system monomer Butyl acrylate 66.70% 100% 30.00% Isooctyl acrylate 13.30% Styrene 15.00% Methyl methacrylate 5.00% Emulsifier Sodium dodecyl sulfate 21.70% 3.50% Emulsifier OS 9.50% Ping Ping O 36.20% TX-30 32.60% Diethylene glycol dimethacrylate 1.00% acrylic acid 4.00% Ammonium persulfate 0.70% water 66.50%

resolve resolution:

Will be equipped with a stirrer, reflux condenser. Place the three-necked flask of the dropping funnel on a constant temperature water bath, add emulsifier and distilled water, stir, raise the temperature to 78-80°C, add the initiator, stir for 0.5 hours, and drop soft/hard monomers, hydrophilic monomers and Pre-crosslinked monomers, keep warm for 1 hour after dropwise addition, then raise the temperature to about 85°C, keep warm for 1 hour, cool down, neutralize with sodium hydroxide or triethylamine, filter, and discharge.

Application Performance of Embodiment 8

Process prescription:

Cotton fabric printing process: paint blue: 50g/l; adhesive: 180g/l; 4% PTF: 400g/l; urea: 20g/l; ammonia water to adjust PH: 7-8; 100 ℃ drying for 3 minutes;

Pure cotton fabric dyeing process: paint blue: 50g/l; binder: 50g/l; JFC: 2g/l; two dipping and two rolling; drying at 100°C for 3 minutes;

Silk dyeing process: paint blue: 50g/l; binder: 100g/l; two dipping and two rolling; drying at 100°C for 3 minutes;

Raw cotton stiffness: 4.6cm

Electric spinning as it is: stiffness: 4.5cm; drape (%): 77%; air flow: 146.31/m ² .s;

Crepe chine as it is: Stiffness: 3.3cm; Drape (%): 45%; Air flow: 1477.25/m ² .s;

Application effect of table 8 adhesive Dry fastness Wet fastness Color fastness Color fastness Apparent depth (k/s) Chroma (c) Stiffness (cm) Drape (%) Air flow (l/m ² .s) cotton print 4 4 19.87 35.78 5.2 cotton dyed 3 3-4 4-5 4 9.92 35.58 5.71 silk dyed Electric spinning 4 4 4-5 4-5 9.86 31.99 5.1 70 727 crepe de chine 4 3-4 5 4 15.18 32.99 4.1 43 1772

Claims (4)

1. A non-baking formaldehyde-free paint dyeing nano-adhesive water-based latex, wherein the adhesive is generated by the reaction of the following ingredients: (1) Pre-crosslinking monomer: ethylene glycol dimethacrylate, ethylene glycol dimethyl acrylate or diethylene glycol dimethyl acrylate; can be alone or mixed use; (2) Soft monomer: butyl acrylate, isooctyl acrylate, heptyl acrylate, pentyl acrylate or hexyl acrylate; can be used alone or in combination; (3) A hard monomer: styrene, methyl methacrylate or acrylonitrile, which can be used alone or in combination; (4) Hydrophilic monomer methacrylic acid; (5) The emulsifier is a compound of anionic surfactant and nonionic emulsifier, the anionic surfactant is sodium lauryl sulfate, the nonionic emulsifier is TX-30, or it has anionic/nonionic A surfactant function or sodium sulfosuccinate with a similar structure, combined with Pingpinga O and emulsifier OS to form a compound system, the ratio of anion/non-emulsifier is 1:1-1:2; and (6) Initiator: ammonium persulfate, potassium persulfate. 2, the preparation method of baking-free formaldehyde-free paint dyeing nano-adhesive water-based latex as claimed in claim 1, is characterized in that comprising the following steps: At 70-90°C, add a certain amount of emulsifier into distilled water, stir evenly, add dropwise the mixed liquid of initiator aqueous solution and pre-crosslinking monomer, soft monomer, hard monomer and hydrophilic monomer according to the formula, add dropwise Complete within 10-50 minutes, react for 01-5 hours, neutralize with ammonia water or organic amine, and filter; the weight ratio of the total weight of the soft monomer and hard monomer, emulsifier and water is 30:3- 3.5:66.5～67; the total weight of soft monomer and hard monomer, the weight ratio of pre-crosslinking monomer, methacrylic acid and initiator is 1:0.004～0.02:0.025～0.050:0.004～0.009, soft monomer The weight ratio with hard monomer is 75～80:20～25. 3. The method for preparing the non-baking formaldehyde-free paint dyeing nano-adhesive aqueous latex as claimed in claim 2, wherein the neutralizing agent is ammonia or organic amine. 4. The application of baking-free formaldehyde-free paint dyeing nano-adhesive aqueous latex as claimed in claim 1, which is characterized in that it is used for textile paint dyeing.

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