CN108997928B - Fluoride-free waterproof agent - Google Patents

Fluoride-free waterproof agent Download PDF

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CN108997928B
CN108997928B CN201711481623.5A CN201711481623A CN108997928B CN 108997928 B CN108997928 B CN 108997928B CN 201711481623 A CN201711481623 A CN 201711481623A CN 108997928 B CN108997928 B CN 108997928B
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waterproof agent
fluorine
free
parts
methyl
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CN108997928A (en
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陈双永
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Dongguan Baisilan Shoe Material Technology Co ltd
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Dongguan Baisilan Shoe Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Abstract

The invention relates to the field of auxiliaries, and particularly relates to a fluorine-free waterproof agent which comprises the following components in parts by weight: 50-90 parts of methyl MQ silicon resin; 10-50 parts of methyl silicone oil; and (4) proper amount of solvent. The invention is based on the environmental protection requirement and the pursuit of green development, and carries out one-time technical innovation and concept breakthrough on the existing waterproof agent. The fluoride-free waterproof agent provided by the invention does not contain fluoride, is inert to organisms, basically has no toxicity or harm, is durable in water resistance, water washing resistance and weathering resistance, is universal and easily available in raw materials, simple and easy in preparation process, green and environment-friendly in process, and free of waste generation due to simple physical mixing without treatment of a reaction furnace. The invention has immeasurable application prospect in green development, and is a green product with great popularization significance in the field of the current waterproof agent.

Description

Fluoride-free waterproof agent
The technical field is as follows:
the invention relates to the field of auxiliaries, in particular to a fluorine-free waterproof agent for fabrics, leather and shoe materials.
Background art:
with the improvement of production and living standards, people have higher and higher requirements on the functionality of fabrics, and waterproof fabrics are one of the fabrics. Water repellents can impart hydrophobic properties to textile surfaces.
The most commercially available water repellent is generally a fluorine-containing water repellent. Fluorine-based water repellents are generally composed of oligomers or polymers having a large number of fluorine-containing groups, and can impart good water and oil repellency to fiber materials.
However, in recent years, due to the environmental ecology problem caused by fluorine-containing compounds and the problem of the influence on human health, there has been an increasing interest in finding a substitute which does not contain fluorine and provides good water-repellent properties.
The invention content is as follows:
in order to overcome the environmental protection factors and technical defects of the existing products, the invention provides the fluorine-free waterproof agent with simple formula and good waterproof effect.
In order to realize the purpose of the invention, the following technical scheme is adopted for realizing the purpose:
a fluorine-free waterproof agent comprises the following components in parts by weight:
components Parts by mass
Methyl MQ silicon resin 50 to 90 portions of
Methyl silicone oil 10 to 50 parts of
Solvent(s) Proper amount of
Currently, for the research on silicone-based water repellent agents, organosiloxanes having polar functional groups, such as methyl-, hydroxyl-, mercapto-, carboxyl-bearing linear or linear-structured polysiloxanes, are mostly used.
In the invention, the methyl MQ silicon resin is a special-structure organic silicon resin consisting of four functional group siloxane chain links (Q) and single functional group siloxane chain links (M), and is a novel organic silicon high polymer material with a three-dimensional (nonlinear) structure and formed by taking Si-O bonds as a framework. The methyl MQ silicon resin has excellent mechanical and chemical stability, moisture resistance and hydrophobic performance, and meanwhile, the light transmission performance is excellent and the air permeability is good. Methyl silicone oil is also called polydimethylsiloxane, is a linear polysiloxane, has special smoothness, flexibility, hydrophobicity and high and low temperature resistance, and is easy to absorb moisture.
The methyl MQ silicon resin is matched with the methyl silicone oil, so that the rigidity of the methyl MQ silicon resin can be reduced, the phenomenon that the material is hardened after treatment can be effectively prevented, and the problems of moisture absorption and material softening of the methyl silicone oil can be solved.
The raw material adopted by the invention is organic silicon, does not contain fluoride, is inert to organisms, and basically has no toxicity or harm, and meanwhile, the product has good waterproof effect, durable waterproof effect, water washing resistance and weather resistance, and is a green and environment-friendly waterproof agent with great market value. In addition, the raw materials adopted by the invention are simple and easy to obtain, and the production cost is low.
Preferably, the fluorine-free waterproof agent comprises the following components in parts by weight:
components Parts by mass
Methyl MQ silicon resin 68 to 88 portions of
Methyl silicone oil 12 to 32 portions of
Solvent(s) Proper amount of
In actual use, the waterproof agent can be diluted by a solvent according to requirements until the solid content is 3% -60%.
Further, the solvent is an ester and/or alkane solvent. The ester solvent is one or more of ethyl acetate and butyl acetate.
In view of the solubility to the methyl MQ silicone resin and the methyl silicone oil, and the influence on the water-repellent base material and pungent odor, an alkane-type solvent is preferable.
Further preferably, the solvent is one or more of isoparaffin. Preferably, the solvent employs isododecane and/or isohexadecane. The isododecane and the isohexadecane belong to cosmetic grade diluents, are colorless and tasteless, almost do not contain aromatic hydrocarbon and sulfur, are friendly to human and environment, are easy to biodegrade, have high isomerization degree, and are safe and environment-friendly.
The invention also provides a preparation method of the fluorine-free waterproof agent, which comprises the following steps:
S1 uniformly mixing methyl MQ silicon resin and a solvent according to a certain proportion;
S2 uniformly mixing the methyl silicone oil and the solvent according to the same proportion as that of the step S1;
S3 and (4) uniformly mixing the mixed liquid obtained in the steps S1 and S2 according to the mass fraction ratio to obtain the fluorine-free waterproof agent.
The preparation methods all adopt simple physical mixing, no chemical reaction is needed, no waste is generated in the preparation process, the preparation process is simple and easy to implement, and the process is green and environment-friendly.
The application method of the product of the invention is to make the waterproof agent permeate into the material to be treated in a soaking, rolling or spraying way.
Compared with the prior art, the invention has the beneficial effects that:
(1) the fluoride-free water-proofing agent provided by the invention is free of fluoride, inert to organisms and basically nonhazardous, has an excellent water-proofing effect, is durable in water-proofing effect, resistant to washing and weathering, and is a green and environment-friendly fluoride-free water-proofing agent with a great market value.
(2) The preparation method of the fluorine-free waterproof agent provided by the invention only needs simple physical mixing of raw materials, does not need chemical reaction, does not generate wastes, has the characteristics of simple and feasible preparation process, green and environment-friendly process and the like, and simultaneously has the remarkable characteristics of good product stability, high reproducibility and the like.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in further detail below.
Example 1
A fluorine-free waterproof agent comprises the following components in parts by weight:
Figure BDA0001533946780000031
wherein the solvent is an ester and/or alkane solvent. The ester solvent is one or more of ethyl acetate and butyl acetate. The alkane solvent is preferably an isoparaffin, such as isododecane, isocetyl.
The preparation method of the fluorine-free waterproof agent comprises the following specific steps:
S1 uniformly mixing methyl MQ silicon resin and a solvent according to a certain proportion;
S2 uniformly mixing the methyl silicone oil and the solvent according to the same proportion as that of the step S1;
S3 and (4) uniformly mixing the mixed liquid obtained in the steps S1 and S2 according to the mass fraction ratio to obtain the fluorine-free waterproof agent.
Example 2
A fluorine-free waterproof agent comprises the following components in parts by weight:
Figure BDA0001533946780000032
example 3
A fluoride-free waterproof agent comprises the following components in parts by weight:
Figure BDA0001533946780000033
example 4
A fluorine-free waterproof agent comprises the following components in parts by weight:
Figure BDA0001533946780000034
example 5
A fluorine-free waterproof agent comprises the following components in parts by weight:
Figure BDA0001533946780000041
example 6
A fluorine-free waterproof agent comprises the following components in parts by weight:
Figure BDA0001533946780000042
comparative example 1
A fluorine-free waterproof agent comprises the following components in parts by weight:
Figure BDA0001533946780000043
comparative example 2
A fluorine-free waterproof agent comprises the following components in parts by weight:
Figure BDA0001533946780000044
test methods and results:
the waterproof effect of the material treated by the waterproof agent provided in examples 1 to 6 and comparative examples 1 to 2 was examined by an anti-siphon test or a surface moisture resistance test of the treated material according to the actual application requirements.
Firstly, sample treatment
The samples were pretreated with the water repellent agents provided in examples 1 to 6 and comparative examples 1 to 2, respectively, and dried for use. The sample preparation requirements for different materials are shown in table 1.
Table 1: preparation of the samples
Figure BDA0001533946780000051
Second, anti-siphon test of shoelace and braid
Figure BDA0001533946780000052
Third, surface moisture resistance test (Water repellent test) of leather, textile cloth
The test method of national standard GB 4745-1997 is adopted for testing.
1. Test flow
1 Funnel with nozzle is placed perpendicularly
2 The leather or cloth keeps an angle of 45 degrees
3 The distance between the nozzle and the central point of the textile fabric or leather is about 15cm
4 250ml of water is required to flow in 25-30 seconds
5 The front side of the leather or cloth was leveled downward, and the sample was observed for wetting by gently patting two times.
2. Test standard
Figure BDA0001533946780000061
Fourth, result analysis
The test results are shown in tables 2 and 3 according to the above test methods.
Table 2: anti-siphon test result of shoelace and braid
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Comparative example 2
Shoe lace Medium and high grade Medium and high grade Good effect Is excellent in Is excellent in Is excellent in Difference (D) Is excellent in
Ribbon Medium and high grade Medium and high grade Good effect Is excellent in Is excellent in Is excellent in Difference (D) Is excellent in
Color change Is composed of Is free of Is free of Is free of Is free of Is free of Is free of Is free of
Variation in hardness Is slightly soft Is slightly soft Light and slight Light and slight Light and slight Is slightly hard Is soft Is hard to be
Table 3: water-proof test result of leather and textile cloth
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Comparative example 2
Leather Grade 3 Grade 3 4 stage 4 stage 4 stage 4 stage 2 4 stage
Textile fabric Grade 3 Grade 3 Grade 4 Grade 4 4 stage 4 stage 2 4 stage
Colour change Is free of Is free of Is free of Is free of Is free of Is free of Is free of Is composed of
Variation in hardness Is slightly soft Is slightly soft Light and slight Light and slight Light and slight Is slightly hard Is soft Is hard to be
The following conclusions are drawn from the test results of tables 2 and 3:
(1) examples 1 and 2 had a moderate water-repellent effect and slightly affected the hardness of the treated material.
(2) Example 6 has a good water-proof effect, and slightly affects the hardness of the treated material.
(3) Examples 3, 4, and 5 have a good waterproof effect and have a small influence on the whole treated material.
(4) Comparative example 1 has a poor waterproof effect and has a large influence on the hardness of the treated material.
(5) Comparative example 2 has a good waterproof effect and has a large influence on the hardness of the treated material.
(6) The waterproof effect is better as the addition amount of the methyl MQ silicon resin is increased, but the hardness of the treated material is obviously increased.
(7) With the increase of the addition amount of the methyl silicone oil, the waterproof effect is poorer, and the softness of the treated material is obviously increased.
(8) In summary, examples 1 and 6 belong to the critical point, and comparative examples 1 and 2 are not ideal; on the other hand, the embodiments 3, 4 and 5 have better overall effects, and therefore the mass fraction ratios of the embodiments 3 to 5 are the most ideal choices.

Claims (5)

1. The fluorine-free waterproof agent is characterized by being prepared by physically mixing the following raw materials in parts by mass:
75 parts of methyl MQ silicon resin;
25 parts of methyl silicone oil;
a proper amount of solvent;
the solvent adopts isododecane and/or isohexadecane;
the fluorine-free waterproof agent is used as a waterproof agent for fabrics, leather and shoe materials;
the preparation method of the fluorine-free waterproof agent comprises the following specific steps:
s1, uniformly mixing methyl MQ silicon resin and a solvent according to a certain proportion;
s2, uniformly mixing the methyl silicone oil and the solvent according to the same proportion as that in the step S1;
s3, uniformly mixing the mixed liquid obtained in the steps S1 and S2 according to the mass fraction ratio to obtain the fluorine-free waterproof agent.
2. The fluorine-free waterproof agent is characterized by being prepared by physically mixing the following raw materials in parts by mass:
88 parts of methyl MQ silicon resin;
12 parts of methyl silicone oil;
a proper amount of solvent;
the solvent adopts isododecane and/or isohexadecane;
the fluorine-free waterproof agent is used as a waterproof agent for fabrics, leather and shoe materials;
the preparation method of the fluorine-free waterproof agent comprises the following specific steps:
s1, uniformly mixing methyl MQ silicon resin and a solvent according to a certain proportion;
s2, uniformly mixing the methyl silicone oil and the solvent according to the same proportion as that in the step S1;
s3, uniformly mixing the mixed solution obtained in the steps S1 and S2 according to the mass fraction ratio to obtain the fluorine-free waterproof agent.
3. The fluorine-free waterproof agent is characterized by being prepared by physically mixing the following raw materials in parts by mass:
90 parts of methyl MQ silicon resin;
10 parts of methyl silicone oil;
a proper amount of solvent;
the solvent adopts isododecane and/or isohexadecane;
the fluorine-free waterproof agent is used as a waterproof agent for fabrics, leather and shoe materials;
the preparation method of the fluorine-free waterproof agent comprises the following specific steps:
s1, uniformly mixing methyl MQ silicon resin and a solvent according to a certain proportion;
s2, uniformly mixing the methyl silicone oil and the solvent according to the same proportion as that of the step S1;
s3, uniformly mixing the mixed liquid obtained in the steps S1 and S2 according to the mass fraction ratio to obtain the fluorine-free waterproof agent.
4. The fluorine-free water repellent agent according to claim 1, 2 or 3, wherein the solid content of the fluorine-free water repellent agent is 3% to 15%.
5. A fluorine-free water repellent agent according to claim 1, 2 or 3, wherein the water repellent agent is impregnated into the material to be treated by spraying, roll coating or dipping.
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CN109371689A (en) * 2018-09-10 2019-02-22 天津大学 Super-hydrophobic polyester oil drawing cloth and preparation method thereof
CN111335041A (en) * 2020-03-13 2020-06-26 东莞市百思兰鞋材科技有限公司 Fluoride-free waterproof agent and preparation method thereof
CN113403856A (en) * 2021-05-27 2021-09-17 安安(中国)有限公司 Processing method of superfine fiber synthetic leather with ultrahigh waterproof and air permeability
CN113668251B (en) * 2021-09-17 2023-08-01 苏州同构科技有限公司 Special waterproof agent for military textile fabric and preparation method

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US8012544B2 (en) * 2003-10-08 2011-09-06 Dow Corning Corporation Silicone MQ resin reinforced silicone elastomer emulsions
US7645333B2 (en) * 2005-12-02 2010-01-12 The Clorox Company Aqueous composition and method for imparting resistance to stain absorption
FR2903113A1 (en) * 2006-06-30 2008-01-04 Rhodia Recherches & Tech EMULSION OIL IN WATER OF AMINOSILOXANES
FR2908420A1 (en) * 2006-11-09 2008-05-16 Rhodia Recherches & Tech SELF-CONTAINING SILICONE COMPOSITION TENABLE TO ELASTOMER
CN103724626B (en) * 2013-12-23 2016-05-18 中昊晨光化工研究院有限公司 A kind of preparation method of MQ silicones
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CN106082773A (en) * 2016-06-06 2016-11-09 湖北新海鸿化工有限公司 A kind of ground waterproofing agent of organosilicon and preparation method thereof

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