Pigment printing pretreatment liquid and preparation method thereof

Abstract

The present application discloses a paint printing pretreatment liquid and a preparation method thereof, and relates to the field of textile treatment agents. The paint printing pretreatment liquid includes acrylic acid monomer, styrene, modified monomer, crosslinking agent, emulsifier, initiator, alcohol and water; acrylic acid monomer includes acrylic acid, alkyl methacrylate, fluorinated acrylate monomer and hydroxy acrylate monomer, and modified monomer includes side chain acrylate modified silicone oil and alkenyl trialkoxy silane; crosslinking agent includes methyl methacrylate ethyl acetoacetate and N-hydroxymethyl acrylamide. The present application can obtain a paint printing pretreatment liquid with good quick-drying property and low water absorption rate through the coordination between the above components, and the paint printing pretreatment liquid is used to pretreat fabrics, which can solve the problem of inconsistent clarity of printed patterns in subsequent fabric printing.

Description

Technical Field

[0001] The present invention relates to the field of textile treatment agents, in particular to a coating printing pretreatment liquid and the like.

[0002] Preparation method. Background Art

[0003] Pigment printing refers to a printing technology that uses paint as a colorant to form patterns on the surface of fabrics. This technology occupies an important position in the textile industry due to its simplicity, speed, and rich colors. Among them, pigment printing pretreatment is an indispensable part of the pigment printing process. It refers to the step of pretreating the fabric with a pigment printing pretreatment liquid before pigment printing. It can improve the surface properties of the fabric and enhance the bonding ability of the paint and the fabric, thereby achieving the purpose of optimizing the printing effect.

[0004] At present, the pretreatment liquid for paint printing in the related technology is mainly acrylate substances. Although acrylate substances have good adhesion to printing paints, the pretreatment liquid for paint printing in the related technology generally has the problems of poor quick-drying or high water absorption after film formation, resulting in inconsistent clarity of subsequent printing patterns. Summary of the invention

[0005] In order to improve the problem of inconsistent print pattern clarity caused by poor quick-drying property or high water absorption of a paint printing pretreatment liquid in the related art, the present application provides a paint printing pretreatment liquid and a preparation method thereof.

[0006] In the first aspect, the present application provides a pigment printing pretreatment liquid adopting the following technical solution:

[0007] A pigment printing pretreatment liquid comprises 180-200 parts by weight of acrylic acid monomer, 5.8-6.4 parts by weight of styrene, 10.5-12.5 parts by weight of modified monomer, 5.7-7.2 parts by weight of crosslinking agent, 1-2 parts by weight of emulsifier, 0.1-0.2 parts by weight of initiator, 150-200 parts by weight of alcohol and 300 parts by weight of water; the acrylic acid monomer comprises acrylic acid, alkyl methacrylate, fluorine-containing acrylate monomer and hydroxy acrylate monomer in a weight ratio of (3-4): (0.5-1): (2-2.5): 3.5; the modified monomer comprises side chain acrylate modified silicone oil and alkenyl trialkoxy silane in a weight ratio of (3-4): 1; the crosslinking agent comprises ethyl methyl acetoacetate and N-hydroxymethyl acrylamide in a weight ratio of 1: (2-3).

[0008] In the present application, the paint printing pretreatment liquid uses a composition including acrylic acid, alkyl methacrylate, fluorinated acrylate monomer and hydroxy acrylate monomer as an acrylic monomer, styrene, side chain acrylate modified silicone oil, alkenyl trialkoxy silane, ethyl acetoacetate methacrylate and N-hydroxymethyl acrylamide are added to participate in the copolymerization reaction of the acrylic monomer, and an emulsifier is used as a stabilizer, and alcohol and water are used together as dispersants. The present application can obtain a paint printing pretreatment liquid with good quick-drying properties and low water absorption through the coordination of the above components. The use of the paint printing pretreatment liquid to pretreat fabrics can solve the problem of inconsistent clarity of printed patterns in subsequent fabric printing.

[0009] Preferably, the alkyl methacrylate is at least one of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate.

[0010] In the present application, the alkyl methacrylate is preferably at least one of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate, which improves the stability of the pigment printing pretreatment liquid while ensuring that the pigment printing pretreatment liquid has good quick drying properties and low water absorption.

[0011] Preferably, the fluorine-containing acrylic ester monomer is at least one of dodecafluoroheptyl methacrylate and tridecafluorooctyl methacrylate.

[0012] In the present application, the fluorine-containing acrylate monomer adopts at least one of dodecafluoroheptyl methacrylate and tridecafluorooctyl methacrylate. Compared with trifluoroethyl methacrylate, hexafluorobutyl methacrylate and heptadecafluorodecyl methacrylate, dodecafluoroheptyl methacrylate and tridecafluorooctyl methacrylate can give the paint printing pretreatment liquid lower water absorption, and at the same time, can protect the main chain and internal molecules, so that the stability of the paint printing pretreatment liquid is better.

[0013] Preferably, the hydroxyacrylate monomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.

[0014] In the present application, the addition of hydroxy acrylate monomer is beneficial to improving the wetting and permeability of the pigment printing pretreatment liquid to the fabric, and has a promoting effect on improving the stability of the printed pattern on the fabric.

[0015] Preferably, the structural formula of the side chain acrylate modified silicone oil is as follows:

[0016]

[0017] The value range of n is 8-15, and the value range of m is 1-2.

[0018] In the present application, the side chain acrylate modified silicone oil is preferably the side chain acrylate modified silicone oil of the above structure, which can further effectively reduce the water absorption rate of the pigment printing pretreatment liquid and ensure the stability of the pigment printing pretreatment liquid.

[0019] Preferably, the alkenyltrialkoxysilane is at least one of vinyltrimethoxysilane, vinyltriethoxysilane, acryltrimethoxysilane and vinyltriisopropoxysilane.

[0020] Preferably, the emulsifier comprises anionic surfactant and nonionic surfactant, and the weight ratio of the anionic surfactant to the nonionic surfactant is 1:(1-1.5).

[0021] In the present application, the emulsifier is a composition of anionic surfactant and nonionic surfactant in a weight ratio of 1: (1-1.5), which is beneficial to further improve the stability of the pigment printing pretreatment liquid.

[0022] Optionally, the anionic surfactant is at least one of sodium dodecyl sulfate and sodium dodecylbenzene sulfonate, and the nonionic surfactant is at least one of polyoxyethylene alkyl ether and polyoxyethylene nonanol ether.

[0023] Optionally, the initiator is at least one of a persulfate initiator and a water-soluble azo initiator.

[0024] In the present application, the initiator is a water-soluble initiator such as persulfate, water-soluble azo initiator, etc., which is conducive to the smooth copolymerization of the components and obtains a pigment printing pretreatment liquid with good stability.

[0025] In the second aspect, the present application provides a method for preparing a pigment printing pretreatment using the following technical solution:

[0026] A method for preparing a pigment printing pretreatment liquid comprises the following steps:

[0027] Mix the initiator with part of water to prepare an initiator solution with a mass concentration of 0.1-0.5%;

[0028] Add acrylic monomer, styrene, modified monomer, crosslinking agent, emulsifier, alcohol and the remaining

[0029] water to obtain a premixed solution;

[0030] Add the initiator solution to the premixed solution and control the temperature at 65-75°C to polymerize to obtain the coating.

[0031] Printing pretreatment liquid.

[0032] The present application first prepares an initiator solution with a mass concentration of 0.1-0.5%, and then drops the initiator solution into the premixed solution, which is conducive to a full reaction between the raw materials and has the characteristics of simple steps, convenient operation and good safety.

[0033] In summary, the present application has at least the following beneficial technical effects:

[0034] (1) In the present application, the pretreatment liquid for pigment printing uses a composition including acrylic acid, alkyl methacrylate, fluorinated acrylic acid ester monomer and hydroxy acrylic acid ester monomer as acrylic acid monomer, adds styrene, side chain acrylic acid modified silicone oil, alkenyl trialkoxy silane, ethyl methyl acetoacetate and N-hydroxymethyl acrylamide to participate in the copolymerization reaction of acrylic acid monomer, and uses an emulsifier as a stabilizer, and alcohol and water as dispersants. Through the coordination of the above components, a pigment printing pretreatment liquid with good quick-drying property and low water absorption can be obtained. The use of the pigment printing pretreatment liquid to pretreat fabrics can solve the problem of inconsistent clarity of printed patterns in subsequent fabric printing.

[0035] (2) The present application first prepares an initiator solution with a mass concentration of 0.1-0.5%, and then drops the initiator solution into the premixed solution, which is conducive to the full reaction between the raw materials and has the characteristics of simple steps, convenient operation and good safety. DETAILED DESCRIPTION

[0036] The present application is further described below in conjunction with specific experiments. Unless otherwise specified, the raw materials used in the present application can be purchased from the market.

[0037] Example

[0038] [Example 1]

[0039] A pigment printing pretreatment liquid comprises the following raw materials:

[0040] Acrylic acid monomer: 180 kg; in this embodiment, the acrylic acid monomer is a composition of acrylic acid, methyl methacrylate, trifluoroethyl methacrylate and hydroxyethyl acrylate, and the weight ratio of acrylic acid, methyl methacrylate, trifluoroethyl methacrylate and hydroxyethyl acrylate is 3:1:2.5:3.5;

[0041] Styrene: 5.8kg;

[0042] Modified monomer: 10.5 kg; In this embodiment, the modified monomer is a composition of side chain acrylate modified silicone oil and vinyl trimethoxy silane, the weight ratio of side chain acrylate modified silicone oil and vinyl trimethoxy silane is 3:1, and the structural formula of the side chain acrylate modified silicone oil is as follows:

[0043]

[0044] Among them, the value of n is 5, and the value of m is 1;

[0045] Cross-linking agent: 5.7 kg; In this embodiment, the cross-linking agent is a composition of ethyl acetoacetate methacrylate and N-hydroxymethyl acrylamide, and the weight ratio of ethyl acetoacetate methacrylate to N-hydroxymethyl acrylamide is 1:2;

[0046] Emulsifier: 1 kg; In this embodiment, the emulsifier is a composition of sodium lauryl sulfate and dodecylphenol polyoxyethylene ether OP-10, and the weight ratio of sodium lauryl sulfate to dodecylphenol polyoxyethylene ether OP-10 is 1:3;

[0047] Initiator: 0.1 kg; in this embodiment, the initiator is specifically sodium persulfate;

[0048] Alcohol: 150kg;

[0049] Water: 300kg.

[0050] In this embodiment, the preparation method of the pigment printing pretreatment liquid comprises the following steps:

[0051] The initiator is mixed with part of water to prepare an initiator solution with a mass concentration of 0.1%;

[0052] Acrylic monomer, styrene, modified monomer, crosslinking agent, emulsifier, alcohol and remaining water are mixed to obtain a premixed liquid; an initiator solution is added dropwise to the premixed liquid, and the temperature is controlled at 65° C. to polymerize for 4 hours to obtain a pigment printing pretreatment liquid.

[0053] [Example 2]

[0054] A pigment printing pretreatment liquid comprises the following raw materials:

[0055] Acrylic acid monomer: 200 kg; in this embodiment, the acrylic acid monomer is a composition of acrylic acid, butyl methacrylate, hexafluorobutyl methacrylate and hydroxyethyl methacrylate, and the weight ratio of acrylic acid, butyl methacrylate, hexafluorobutyl methacrylate and hydroxyethyl methacrylate is 4:0.5:2:3.5;

[0056] Styrene: 6.4kg;

[0057] Modified monomer: 12.5 kg; In this embodiment, the modified monomer is a composition of side chain acrylate modified silicone oil and acryltrimethoxysilane, the weight ratio of side chain acrylate modified silicone oil and acryltrimethoxysilane is 4:1, and the structural formula of the side chain acrylate modified silicone oil is as follows:

[0058]

[0059] Among them, the value of n is 5, and the value of m is 2;

[0060] Cross-linking agent: 7.2 kg; in this embodiment, the cross-linking agent is a composition of ethyl acetoacetate methacrylate and N-hydroxymethyl acrylamide, and the weight ratio of ethyl acetoacetate methacrylate to N-hydroxymethyl acrylamide is 1:3;

[0061] Emulsifier: 2 kg; In this embodiment, the emulsifier is a composition of sodium lauryl sulfate and dodecylphenol polyoxyethylene ether OP-10, and the weight ratio of sodium lauryl sulfate to dodecylphenol polyoxyethylene ether OP-10 is 1:3;

[0062] Initiator: 0.2 kg; in this embodiment, the initiator is specifically sodium persulfate;

[0063] Alcohol: 200kg;

[0064] Water: 300kg.

[0065] In this embodiment, the preparation method of the pigment printing pretreatment liquid comprises the following steps:

[0066] The initiator is mixed with part of water to prepare an initiator solution with a mass concentration of 0.2%;

[0067] Acrylic monomer, styrene, modified monomer, crosslinking agent, emulsifier, alcohol and remaining water are mixed to obtain a premixed liquid; an initiator solution is added dropwise to the premixed liquid, and the temperature is controlled at 75° C. to polymerize for 3 hours to obtain a pigment printing pretreatment liquid.

[0068] [Example 3]

[0069] A pigment printing pretreatment liquid, which differs from [Example 1] in that the fluorine-containing acrylate monomer is different.

[0070] In this embodiment, the fluorine-containing acrylate monomer is dodecafluoroheptyl methacrylate.

[0071] [Example 4]

[0072] A pigment printing pretreatment liquid, which differs from [Example 1] in that the fluorine-containing acrylate monomer is different.

[0073] In this embodiment, the fluorine-containing acrylic acid ester monomer is heptadecafluorodecyl methacrylate.

[0074] [Example 5]

[0075] A pigment printing pretreatment liquid, which differs from [Example 3] in that the side chain acrylate modified silicone oil is different.

[0076] In this embodiment, the structural formula of the side chain acrylate modified silicone oil is as follows:

[0077]

[0078] Among them, the value of n is 10 and the value of m is 1.

[0079] [Example 6]

[0080] A pigment printing pretreatment liquid, which differs from [Example 3] in that the side chain acrylate modified silicone oil is different.

[0081] In this embodiment, the structural formula of the side chain acrylate modified silicone oil is as follows:

[0082]

[0083] Among them, the value of n is 25 and the value of m is 1.

[0084] Comparative Example

[0085] [Comparative Example 1]

[0086] A pigment printing pretreatment liquid, which is different from [Example 1] in that the proportions of the components in the acrylic acid monomer are different.

[0087] In this comparative example, the weight ratio of acrylic acid, methyl methacrylate, trifluoroethyl methacrylate and hydroxyethyl acrylate is 3:5:1:1.

[0088] [Comparative Example 2]

[0089] A pigment printing pretreatment liquid, which differs from [Example 1] in that the ratios of the components in the modified monomer are different.

[0090] In this comparative example, the weight ratio of the side chain acrylate modified silicone oil to vinyl trimethoxy silane is 9:1.

[0091] [Comparative Example 3]

[0092] A pigment printing pretreatment liquid, which differs from [Example 1] in that the ratios of the components in the cross-linking agent are different.

[0093] In this comparative example, the weight ratio of ethyl acetoacetate methacrylate to N-hydroxymethyl acrylamide is 4:1.

[0094] Performance test surface drying time: refer to the standard GB / T 1728-2020 "Determination of Drying Time of Paint Film and Putty Film" and use the finger touch method to determine the surface drying time of the paint printing pretreatment liquid. Apply the prepared paint printing pretreatment liquid on the tinplate polished with sandpaper, and then place it horizontally at normal temperature and pressure. Every 5 minutes, touch the surface of the paint printing pretreatment liquid with your finger in an area not less than 1 cm from the edge of the sample. When it feels a little sticky but no emulsion sticks to the finger, it is considered that the surface of the paint printing pretreatment liquid is dry. Record the surface drying time of the paint printing pretreatment liquid in Table 1.

[0095] Water absorption rate: The paint printing pretreatment liquid in each embodiment and comparative example is sprayed onto a substrate. After drying, the film formed by the paint printing pretreatment liquid is removed from the substrate, and the weight m1 of the film formed by each embodiment and comparative example is weighed. Then, the film is immersed in distilled water for 48 hours. After being taken out, the moisture on the film is absorbed with filter paper, and then the weight m2 of the film after immersion in each embodiment and comparative example is weighed. The water absorption rate of the paint printing pretreatment liquid after film formation in each embodiment and comparative example is calculated by the formula water absorption rate = (m2-m1) / m1*100%, and the water absorption rate is recorded in the following Table 1.

[0096] Printing pattern quality: The paint printing pretreatment liquid in each embodiment and comparative example was evenly sprayed onto the polyester fabric, and after drying at 60°C for 5 seconds, the pretreated polyester fabric was printed with paint printing by screen printing technology and dried. Then, 10 finished products obtained by the paint printing pretreatment liquid corresponding to each embodiment and comparative example were randomly selected and compared with the standard printing pattern, and the number of products that were consistent with the standard printing pattern in clarity and integrity was recorded, and recorded in the following Table 1.

[0097] Stability of the paint printing pretreatment liquid: The printing pretreatment liquid obtained in each embodiment and the comparative example was subjected to mechanical stability and freeze-thaw stability tests. In the mechanical stability test, the speed of the centrifuge was 2500r / min and 5000r / min, and the dispersion time was 1h, and the paint printing pretreatment liquid was observed to see whether demulsification occurred; in the freeze-thaw stability test, the paint printing pretreatment liquid was placed in a low-temperature box at -5°C, taken out after 18h, and placed at 25°C for 6h, and the freeze-thaw cycle was repeated 20 times to observe whether demulsification occurred in the paint printing pretreatment liquid, and the results were recorded in Table 2 below.

[0098] Table 1

[0099]

[0100] Table 2

[0101]

[0102]

[0103] Combining Example 1 with Comparative Examples 1-3 and the results in Table 1-2, it can be seen that in the present application, a paint printing pretreatment liquid with good quick-drying property and low water absorption is obtained by reacting a specific ratio of acrylic acid, alkyl methacrylate, fluorinated acrylate monomer, hydroxy acrylate monomer, styrene, side chain acrylate modified silicone oil, alkenyltrialkoxysilane, ethyl methacrylate acetate and N-hydroxymethylacrylamide. The paint printing pretreatment liquid can be dried in 5 seconds at 60°C. When printing on a fabric pretreated with the paint printing pretreatment liquid, a printing pattern with consistent pattern clarity can be obtained.

[0104] Combining Example 1 with Examples 3-4 and the results in Table 1-2, it can be seen that compared with trifluoroethyl methacrylate and heptadecafluorodecyl methacrylate, the fluorinated acrylate monomer using dodecafluoroheptyl methacrylate can give the paint printing pretreatment liquid lower water absorption, and at the same time, can protect the main chain and internal molecules, so that the stability of the paint printing pretreatment liquid is better.

[0105] Combining Example 3 with Examples 5-6 and the results in Table 1-2, it can be seen that the side chain acrylate modified silicone oil preferably has an n value of 8-15 and an m value of 1-2, which can further effectively reduce the water absorption rate of the paint printing pretreatment liquid while ensuring the stability of the paint printing pretreatment liquid.

[0106] This specific implementation manner is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the specific implementation manner as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A pigment printing pretreatment liquid, characterized in that: The invention comprises 180-200 parts by weight of acrylic acid monomer, 5.8-6.4 parts by weight of styrene, 10.5-12.5 parts by weight of modified monomer, 5.7-7.2 parts by weight of crosslinking agent, 1-2 parts by weight of emulsifier, 0.1-0.2 parts by weight of initiator, 150-200 parts by weight of alcohol and 300 parts by weight of water; the acrylic acid monomer comprises acrylic acid, alkyl methacrylate, fluorine-containing acrylate monomer and hydroxy acrylate monomer in a weight ratio of (3-4):(0.5-1):(2-2.5):3.5, the modified monomer comprises side chain acrylate modified silicone oil and alkenyltrialkoxysilane in a weight ratio of (3-4):1; the crosslinking agent comprises ethyl acetoacetate methacrylate and N-hydroxymethyl acrylamide in a weight ratio of 1:(2-3); the fluorine-containing acrylate monomer is at least one of dodecafluoroheptyl methacrylate and tridecafluorooctyl methacrylate; The structural formula of the side chain acrylate modified silicone oil is as follows: The value range of n is 8-15, and the value range of m is 1-2.

2. A pigment printing pretreatment liquid according to claim 1, characterized in that: The alkyl methacrylate is at least one of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate.

3. A pigment printing pretreatment liquid according to claim 1, characterized in that: The hydroxy acrylate monomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.

4. A pigment printing pretreatment liquid according to claim 1, characterized in that: The alkenyltrialkoxysilane is at least one of vinyltrimethoxysilane, vinyltriethoxysilane, acryltrimethoxysilane and vinyltriisopropoxysilane.

5. A pigment printing pretreatment liquid according to claim 1, characterized in that: The emulsifier comprises an anionic surfactant and a nonionic surfactant, and the weight ratio of the anionic surfactant to the nonionic surfactant is 1:(1-1.5).

6. A pigment printing pretreatment liquid according to claim 5, characterized in that: The anionic surfactant is at least one of sodium dodecyl sulfate and sodium dodecylbenzene sulfonate, and the nonionic surfactant is at least one of polyoxyethylene alkyl ether and polyoxyethylene nonanol ether.

7. A pigment printing pretreatment liquid according to claim 1, characterized in that: The initiator is at least one of a persulfate initiator and a water-soluble azo initiator.

8. The method for preparing a pigment printing pretreatment liquid according to any one of claims 1 to 7, characterized in that: The following steps are involved: Mix the initiator with part of water to prepare an initiator solution with a mass concentration of 0.1-0.5%; Mixing acrylic monomer, styrene, modified monomer, cross-linking agent, emulsifier, alcohol and remaining water to obtain a premixed solution; The initiator solution is added dropwise to the premixed liquid, and the temperature is controlled at 65-75° C. to carry out polymerization to obtain a pigment printing pretreatment liquid.

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