CN104233818B - Organosilicon water repellent and its preparation and application - Google Patents

Abstract

The present invention relates to a kind of organosilicon water repellent, the component of following weight is contained in every liter of finishing agent：Self-crosslinking 25~80g of organic silicone finishing agent, 7~20g of organosilicon cross-linking agent, 0.01~0.1g of alkali, remaining is deionized water.The durable water repellent that the organosilicon water repellent of the present invention is mainly used in cotton, terylene, nylon and its blended fabric finishing process in printing and dye-ing arranges, while assigns the good resilience of fabric and plentiful feel；Due to not fluorine-containing and solvent in organic silicone finishing agent, all it is safe from harm to human body and environment, and stablize in storage and transportational process property retention, it is a kind of environmentally protective water repellent, thus is with a wide range of applications and prospect in terms of the organic silicone finishing agent of the present invention is industrially particularly textile water repellent finish.

Description

Silicone water repellent and its preparation and application

technical field

The invention relates to the field of preparation and application of organosilicon finishing agents, in particular to an organosilicon water-repellent agent and its preparation and application.

Background technique

During the chemical processing of fabrics, its hydrophilicity is a crucial performance. In the process of wearing fabrics, hydrophilicity is also one of the indispensable and important indicators of wearing comfort. However, in some use cases, such as rainy weather, fishing, field and water work and other personnel's outerwear, it is desirable that the fabric should have good water repellency. The water-repellent processing of textiles is also one of the important topics that textile chemical processors have been devoting to research and development for a long time. With the improvement of people's living standards, people's demand for water-repellent fabric products such as outdoor bags, jackets and tents is increasing. Water repellency (hydrophobic) is the deposition of compounds with hydrophobic groups on the surface of fibers, or the reaction of compounds with hydrophobic groups and reactive groups on the surface of fibers, so that the fabric still retains fine pores, that is, only reduces the surface of the fabric (free) capable products.

At present, water repellents for fabrics are mainly divided into three categories: reactive aliphatic compounds, organosilicon compounds and organofluorine compounds. Reactive aliphatic compounds are limited in application to fabrics due to their mediocre water repellency and poor hand feeling after finishing. Most of the organic fluorine water-repellent finishing agents currently used in the market are organic fluorine compounds based on perfluorooctyl sulfonphthalein (PFOS) or other perfluoroalkyl compounds containing 8 carbons or even longer carbon chains. PFOS is a serious hazard to the environment and the human body. The U.S. Environmental Protection Agency and the European Commission have successively issued regulations on the sale and use of PFOS. PFOS will be eliminated in 2015. After 2005, some companies in Europe and Japan replaced C8 with C6 and launched new products that do not contain PFOS and PFOA. However, at present, C6 has general water repellency, poor durability, and is relatively expensive. Silicone water repellent has good water repellency, air permeability and washability, and it is also a good softener. Durable water-repellent effect, so this kind of water-repellent agent is widely used at present, and is favored by the textile industry. The traditional silicone water repellent is under the action of organometallic catalysts and high temperature to polarize the main chain of silicon oxygen, and the polar part and the polar group on the fiber are combined by electrostatic attraction, and the polar group is combined with the fiber. At the same time, the non-polar hydrophobic hydrocarbon groups rotate directionally and are arranged continuously and neatly on the outermost layer of the fiber, so as to achieve the water repellent effect. However, because the combination between this type of silicone water repellent and the fiber is an intermolecular force, the washing resistance is poor. The chloride of polydimethylsilicone oil (PDMS) can be hydrolyzed in sodium hydroxide to produce a crosslinking reaction, and at the same time it is covalently bonded to the fiber, which has a certain effect on improving the washability of the finished textiles, but polydimethylsiloxane The chloride of silicone oil (PDMS) has poor stability and is greatly limited in practical applications. However, polydimethylsilicone oil (PDMS) itself has no active groups, and can only be cross-linked through methyl oxidation at high temperatures (250 ° C ~ 300 ° C), and has poor adhesion to fabrics. Generally, it is not suitable as a fabric repellent alone. Water finishing agent. The silicon-hydrogen bond in polymethyl hydrogen-containing silicone oil (PMS) has high activity. Under the action of catalyst, it is easy to undergo hydrolysis reaction. The Si-OH bond formed by hydrolysis can be dehydrated and condensed by itself, cross-linked into an elastic film, or combined with The hydroxyl groups on the cellulose react to form ether bonds, forming a layer of highly cross-linked polysiloxane film on the surface of the fiber, thereby obtaining good water repellency and becoming the main body of the silicone water repellent. However, polymethylhydrosiloxane (PMS) has two defects. One, the film formed on the surface of the fiber is brittle, which makes the fabric feel rough. Therefore, it cannot be used alone, but must be combined with polydimethylsiloxane. (PDMS) or α, ω-dihydroxy dimethyl silicone oil (hydroxyl silicone oil) mixed application, according to Dow Corning's early patents, the best mixing ratio of PMS/PDMS is 40/60-60/40; second, it is in storage and Hydrogen gas is easily released during transportation, so it has certain dangers.

Contents of the invention

The technical problem to be solved by the present invention is to provide a silicone water-repellent agent and its preparation and application. The silicone water-repellent agent is mainly used for durable water-repellent finishing in the printing and dyeing of cotton, polyester, nylon and their blended fabrics, and at the same time endows the fabric with good resilience and plump hand feeling; since the silicone finishing agent does not contain fluorine and The solvent is harmless to the human body and the environment, and its performance remains stable during storage and transportation. It is a green and environmentally friendly water-repellent agent. Therefore, the organic silicon water-repellent agent of the present invention has industrial advantages, especially in the water-repellent finishing of textiles. Extensive application value and prospect.

The purpose of the present invention is to realize through the following technical solutions:

The purpose of the present invention is to provide a silicone water-repellent agent, which contains the following components per liter of finishing agent: self-crosslinking silicone finishing agent 25-80g, silicone cross-linking agent 5-20g, alkali 0.01-0.1 g, the rest is deionized water.

Described self-crosslinking organosilicon finishing agent, its structural formula is as follows:

R ₁ = -H or -CH ₃

_{R2 = -OCH3 , -OCH2CH3 , -OCH2CH2CH3 , -CH2CH2CH2NH2 , -CH2CH2NHCH2CH2CH2NH2 , or _ _ _ _}

R ₃ =-H or -CH ₃ ;

R ₄ =-CH ₃ ,-OH,-OCH ₃ or-OCH ₂ CH ₃ ;

Among them, x=10～200, y=30～2000, z=10～200.

Described organosilicon crosslinking agent, its structural formula is as follows:

where n=10～200

The alkali is sodium hydroxide, sodium carbonate, ammonia or urea.

The silicone water-repellent agent preferably contains the following components per liter of finishing agent: 60 g of self-crosslinking silicone finishing agent, 12 g of silicone crosslinking agent, 0.04 g of alkali, and the rest is deionized water.

The silicone water-repellent agent preferably contains the following components per liter of finishing agent: 80 g of self-crosslinking silicone finishing agent, 20 g of silicone crosslinking agent, 0.1 g of alkali, and the rest is deionized water.

The silicone water-repellent agent preferably contains the following components per liter of finishing agent: 40 g of self-crosslinking silicone finishing agent, 7 g of silicone crosslinking agent, 0.01 g of alkali, and the rest is deionized water.

The silicone water-repellent agent preferably contains the following components per liter of finishing agent: 25 g of self-crosslinking silicone finishing agent, 5 g of silicone crosslinking agent, 0.05 g of alkali, and the rest is deionized water.

Another object of the present invention is to provide a method for preparing a silicone water repellent, which includes the following steps: 25-80 g of a self-crosslinking silicone finishing agent, 5-20 g of a silicone cross-linking agent and 0.01-0.1 g of an alkali, Add deionized water at room temperature, stir evenly, and set the volume to 1 L to prepare a silicone water repellent agent.

Another object of the present invention is to provide an application of a silicone water-repellent agent, including: using the above-mentioned silicone water-repellent agent, and adopting a padding or dipping finishing process to perform water-repellent finishing on the fabric, and the process parameters: the fabric carrying rate 30-100%, pre-bake at 95-105°C for 90-120 seconds, and bake at 160-190°C for 25-120 seconds.

The preferred process parameters for water-repellent finishing are: the liquid-carrying rate of the fabric is 60%, pre-baking at 100°C for 90 seconds, and baking at 170°C for 60 seconds.

The invention not only carries out cross-linking modification to the finishing agent, but also carries out organosilicon modification treatment at the same time.

Compared with the prior art, the present invention has the following beneficial effects:

1) The silicone water-repellent agent of the present invention is mainly used for durable water-repellent finishing in the printing and dyeing finishing of cotton, polyester, nylon and their blended fabrics, and at the same time imparts good resilience and plump hand feeling to the fabric;

2) Since the silicone water repellent does not contain fluorine and solvents, it is harmless to the human body and the environment, and its performance remains stable during storage and transportation. It is a green and environmentally friendly water repellent. Therefore, the silicone water repellent of the present invention Water agent has wide application value and prospect in industry, especially in textile water-repellent finishing.

Detailed ways

The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

The used fabric of specific embodiment is white cotton poplin (40 * 40,120 * 80), polyester taffeta, nylon silk spinning.

Finishing process: preparation of water-repellent finishing solution → padding finishing solution (one dipping and one rolling) → pre-baking (100℃×90s) → baking → pre-shrinking (overfeeding about 1%) → finished product

Raw materials used in the following examples:

Self-crosslinking silicone finishing agent is provided by Shanghai Fluorochemical Products Co., Ltd., product model SS6152

The organosilicon crosslinking agent was provided by Shanghai Fluorochemical Products Co., Ltd., product model SS6175.

Example 1

Mix 60 g of self-crosslinking silicone finishing agent, 12 g of silicone crosslinking agent, and 0.04 g of sodium hydroxide, add deionized water at room temperature, stir evenly and set the volume to 1 L to prepare silicone water repellent agent.

The process parameters of water-repellent finishing are: the fabric used is white poplin, the liquid carrying rate of the fabric is 70%, the baking temperature is 170°C, and the baking time is 60s.

Example 2

Mix 80 g of self-crosslinking silicone finishing agent, 20 g of silicone crosslinking agent, and 0.1 g of sodium carbonate, add deionized water at room temperature, stir evenly and set the volume to 1 L to prepare silicone water repellent agent.

The process parameters of water-repellent finishing are: the fabric used is polyester taffeta, the liquid carrying rate of the fabric is 30%, the baking temperature is 160°C, and the baking time is 120s.

Example 3

Mix 40 g of self-crosslinking silicone finishing agent, 7 g of silicone crosslinking agent, and 0.01 g of ammonia water, add deionized water at room temperature, stir evenly and set the volume to 1 L to prepare silicone water repellent agent.

The process parameters of water-repellent finishing are: the fabric used is nylon, the liquid carrying rate of the fabric is 30%, the baking temperature is 190°C, and the baking time is 25s.

Example 4

Add 25 g of self-crosslinking silicone finishing agent, 5 g of silicone crosslinking agent, and 0.05 g of urea, add deionized water at room temperature, stir evenly and set the volume to 1 L to prepare silicone water repellent agent.

The process parameters of water-repellent finishing are as follows: the fabric used is white poplin, the liquid carrying rate of the fabric is 60%, the baking temperature is 180°C, and the baking time is 45s.

Carry out following performance test to the processed product of above-mentioned embodiment 1-4:

(1) Water repellency level

Measured according to AATCC22-2001 "Water Repellency Test: Spray Method".

(2) Household washing.

Measured in accordance with GB/T8629-2001 "Household Washing and Drying Procedures for Textile Testing".

The application performance test results of the silicone water repellents prepared in Examples 1-5 are shown in Table 1 below.

Table 1 Application performance table of silicone water repellent

It can be seen from the above table that the silicone water-repellent agent of the present invention makes the fabric have better water-repellent effect, and at the same time has excellent washability and soft hand feeling, and is a green and environmentally friendly durable water-repellent agent.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments, and those skilled in the art can also make various equivalents without violating the spirit of the present invention. These equivalent modifications or replacements are all included within the scope defined by the claims of the present application.

Claims (9)

1. a kind of organosilicon water repellent, the component of following weight is contained in every liter of finishing agent：Self-crosslinking organic silicone finishing agent 25~ 80g, 5~20g of organosilicon cross-linking agent, 0.01~0.1g of alkali, remaining is deionized water；

The self-crosslinking organic silicone finishing agent, its structural formula are as follows：

R₁=-H or-CH₃

R₂=-OCH₃,-OCH₂CH₃,-OCH₂CH₂CH₃,-CH₂CH₂CH₂NH₂,-CH₂CH₂NHCH₂CH₂CH₂NH₂, or

R₃=-H or-CH₃；

R₄=-CH₃,-OH,-OCH₃Or-OCH₂CH₃；

Wherein x=10~200, y=30~2000, z=10~200；

The organosilicon cross-linking agent, its structural formula are as follows：

Wherein n=10~200.

A kind of 2. organosilicon water repellent according to claim 1, it is characterised in that：The alkali is sodium hydroxide, carbonic acid Sodium, ammonium hydroxide or urea.

A kind of 3. organosilicon water repellent according to claim 1, it is characterised in that：The organosilicon water repellent, every liter Contain the component of following weight in finishing agent：Self-crosslinking organic silicone finishing agent 60g, organosilicon cross-linking agent 12g, alkali 0.04g, remaining For deionized water.

A kind of 4. organosilicon water repellent according to claim 1, it is characterised in that：The organosilicon water repellent, every liter Contain the component of following weight in finishing agent：Self-crosslinking organic silicone finishing agent 80g, organosilicon cross-linking agent 20g, alkali 0.1g, remaining For deionized water.

A kind of 5. organosilicon water repellent according to claim 1, it is characterised in that：The organosilicon water repellent, every liter Contain the component of following weight in finishing agent：Self-crosslinking organic silicone finishing agent 40g, organosilicon cross-linking agent 7g, alkali 0.01g, remaining For deionized water.

A kind of 6. organosilicon water repellent according to claim 1, it is characterised in that：The organosilicon water repellent, every liter Contain the component of following weight in finishing agent：Self-crosslinking organic silicone finishing agent 25g, organosilicon cross-linking agent 5g, alkali 0.05g, remaining For deionized water.

7. a kind of preparation method of organosilicon water repellent according to claim 1, includes the following steps：Self-crosslinking is organic Silicon 0.01~0.1g of 25~80g of finishing agent, 5~20g of organosilicon cross-linking agent and alkali, adds deionized water stirring under normal temperature condition 1L uniformly is settled to, organosilicon water repellent is made.

8. a kind of application of organosilicon water repellent according to claim 1, including：Using the organosilicon water repellent, Using pad or dip finishing technique to fabric carry out water repellent finish, technological parameter：Fabric liquid carrying rate for 30~100%, 95~ 105 DEG C of preliminary dryings 90~120 seconds, 160 DEG C~190 DEG C bake 25~120 seconds.

A kind of 9. application of organosilicon water repellent according to claim 8, it is characterised in that：The water repellent finish of waterproof Parameter is：The liquid carrying rate of fabric is 60%, and 100 DEG C of preliminary dryings 90 seconds, 170 DEG C bake 60 seconds.