JPH05214325A - Water-repellent and oil-repellent composition - Google Patents

Abstract

PURPOSE:To provide an excellent water-repellent and oil-repellent composition which can develop high durability which is unattainable by conventional compositions. CONSTITUTION:The water-repellent and oil-repellent composition contains a copolymer (C) composed of (A) a polyfluoroalkyl (meth) acrylate and (B) a urethane bond-containing (meth)acrylate, as essential monomer components, and (D) a blocked polyisocyanate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water and oil repellent agent which is particularly effective in imparting water and oil repellency with high durability.

[0002]

2. Description of the Related Art In recent years, clothing has been actively treated for water and oil repellency, and various compositions have been provided according to the purpose. In sports clothing, water and oil repellency requires high durability against washing and dry cleaning, and in order to obtain this durability,
Polyfluoroalkyl group-containing acrylate and vinyl chloride copolymer (Japanese Patent Publication No. 50-3438), N-methylolacrylamide as a crosslinking component in addition to these monomers,
Copolymers obtained by copolymerizing glycidyl acrylamide and the like have been proposed.

Further, as an additive, a copolymer containing a functional component which is stable to water at room temperature and liberates an --NCO group at high temperature (JP-A-54-131579), a conventional water and oil repellent agent. A water- and oil-repellent agent in which a blocked polyisocyanate compound is mixed in (JP-A-54-133486), an acrylate copolymer containing a polyfluoroalkyl group and a blocked isocyanate group (JP-A-3-8873) ) Has been proposed, but at present the satisfactory durability has not been obtained.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to newly provide a water / oil repellent composition which has not been heretofore known and which provides high durability.

[0005]

The present invention is the following invention made to solve the above-mentioned problems.

Acrylate or methacrylate (A) containing a polyfluoroalkyl group and polyacrylate or polymethacrylate (B) having a urethane bond
A water and oil repellent composition comprising a copolymer (C) obtained by copolymerizing at least two types of monomers containing as essential components, and a blocked polyisocyanate compound (D).

(A) in the present invention is a "polyfluoroalkyl group-containing acrylate or methacrylate", and is hereinafter referred to as a polyfluoroalkyl group-containing (meth).
Also called acrylate. In the following, (meta)
Acrylate means both acrylate and methacrylate. The polyfluoroalkyl group-containing (meth) acrylate (A) is a compound having one acryloyloxy group or a methacryloyloxy group and at least one polyfluoroalkyl group.

The polyfluoroalkyl group (hereinafter sometimes referred to as R _f ) is a linear or branched alkyl group having 2 or more fluorine atoms and having 1 to 2 carbon atoms.
It is 0, preferably 4 to 16. A polyfluoroalkyl group in which 80% or more of the number of hydrogen atoms in an ordinary alkyl group is substituted with fluorine atoms is preferable, and a polyfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms (that is, a perfluoroalkyl group ) Is most preferred. In some cases, a small number of other atoms (such as chlorine atoms as well as hydrogen atoms) other than the fluorine atom may be bonded to the carbon atom, and an oxygen atom may be present between the carbon-carbon bonds. (That is, it may have an oxypolyfluoroalkylene group in other words). As the perfluoroalkyl group, a linear one is preferable, and it is represented by C _n F _{2n + 1} (where n is preferably 4 to 16, particularly preferably 6 to 12).

A binding group is preferably present between the polyfluoroalkyl group and the acryloyloxy group or the methacryloyloxy group, and this binding group is preferably an alkylene group or another divalent binding group as shown in the following specific examples. .. This linking group is not limited to these examples,
Various linking groups known in the known polyfluoroalkyl group-containing (meth) acrylate can be adopted.

As described above, a known compound can be used as the polyfluoroalkyl group-containing (meth) acrylate (A) in the present invention. Further, as (A), two or more kinds of compounds can be used in combination. In particular, the polyfluoroalkyl group-containing (meth) acrylate actually used is often a mixture of two or more compounds having different carbon numbers in the polyfluoroalkyl group portion, and such a mixture is also used in the present invention. It is preferably used.

Specific examples of the polyfluoroalkyl group-containing (meth) acrylate (A) are shown below, but the invention is not limited thereto. In the chemical formula below, R ¹ represents a hydrogen atom or a methyl group, and R _f represents a polyfluoroalkyl group (particularly a perfluoroalkyl group).

CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ R _f CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ N (C ₃ H ₇ ) COR _f CH ₂ = C (R ¹ ) COOCH (CH ₃ ) CH ₂ R _f CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ N (CH ₃ ) SO ₂ R _f CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ N (CH ₃ ) COR _f CH ₂ = C ( R ¹ ) COOCH ₂ CH ₂ N (C ₃ H ₇ ) SO ₂ R _f CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ N (C ₂ H ₅ ) COR _f CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ N (C ₃ H ₇ ) SO ₂ R _f CH ₂ = C (R ¹ ) COOCH (CH ₂ Cl) CH ₂ OCH ₂ CH ₂ N (CH ₃ ) SO ₂ R _f

(B) in the present invention is a "polyacrylate or polymethacrylate having a urethane bond", and is also referred to as a urethane bond-containing poly (meth) acrylate hereinafter. The urethane bond-containing poly (meth) acrylate (B) is a compound having at least two acryloyloxy groups or methacryloyloxy groups and at least one urethane bond. Furthermore, this (B)
Preferably has no free or blocked isocyanate groups. Further, in the present invention, two or more kinds of (B) can be used in combination.

The (B) in the present invention is a hydroxyl group-containing (meth) acrylate and a polyisocyanate compound (2
It is preferably a reaction product with the above organic compound having an isocyanate group). In particular, a reaction product of a (meth) acrylate having one hydroxyl group and a polyisocyanate compound having two to three isocyanate groups is preferable. More preferable (B) is a reaction product of a hydroxyalkyl (meth) acrylate and a diisocyanate compound. Further, this (B) can also be regarded as a polyester of a polyhydroxy compound having a urethane bond and acrylic acid or methacrylic acid.

The hydroxyl group-containing (meth) acrylate is
A mono- or poly-ester of a polyhydric alcohol and (meth) acrylic acid, which is a compound having at least one hydroxyl group. Preferred are monoesters of dihydric alcohols (that is, diols) and (meth) acrylic acid, particularly monoesters of alkylene diols and (meth) acrylic acid, that is, hydroxyalkyl (meth) acrylates. As the alkylene diol,
For example, ethylene glycol, diethylene glycol,
Examples include propylene glycol, dipropylene glycol, butanediol, hexanediol.

As the polyisocyanate compound, aromatic, aliphatic, alicyclic, or other polyisocyanate compounds, and modified products thereof can be used. Specifically, for example, tolylene diisocyanate,
Diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and trimethylolpropane of these diisocyanate compounds Examples include modified products, isocyanurate ring modified products, and addition products with polyhydric alcohols such as glycerin.

This (B) is preferably a compound represented by the general formula (1), that is, a reaction product of a (meth) acrylate having one hydroxyl group and a diisocyanate compound. [CH ₂ = C (R ¹ ) -COO-R ² -O-CO-NH-] ₂ R ³ (1) where R ¹ is a hydrogen atom or a methyl group, and R ² is a diol in which the hydroxyl group is removed. And R ³ represents a residue obtained by removing an isocyanate group from a diisocyanate compound.

In the general formula (1), R ² has ² carbon atoms.
The above alkylene group and polyoxyalkylene group are preferable, and a polyoxyalkylene group formed by repeating an alkylene group having 2 to 6 carbon atoms and an oxyalkylene group having 2 to 6 carbon atoms is particularly preferable. R ³ is preferably a residue obtained by removing two isocyanate groups from a diisocyanate compound selected from tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

As the compound (B), a preferred compound after the compound represented by the general formula (1) is one molecule of a trimethylolpropane-modified diisocyanate compound or a modified isocyanurate ring compound and one hydroxyl group. Have (meta)
It is a reaction product with 3 molecules of acrylate.

In the present invention, in the copolymerization of the above (A) and (B), one kind of monomer having a radically polymerizable unsaturated bond (hereinafter referred to as a copolymerizable monomer) other than these two kinds of monomers. The above may be copolymerized with (A) and (B). Examples of suitable copolymerizable monomers include, but are not limited to, the following monomers. Preferred copolymerizable monomers are vinyl chloride and (meth) acrylates other than the following (A) and (B). Particularly preferred copolymerizable monomers are vinyl chloride and stearyl acrylate.

(Meth) acrylates 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, poly (oxyalkylene) (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, benzyl (meth) acrylate, isocyanate ethyl (meth) acrylate,
Aziridinyl (meth) acrylate, a (meth) acrylate having a polysiloxane.

Other copolymerizable monomers: ethylene, butadiene, isoprene, chloroprene, vinyl acetate, vinyl halides such as vinyl chloride and vinyl fluoride, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, (Meth) acrylamide, diacetone (meth) acrylamide, methylolated (meth) acrylamide, N-methylol (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, maleic anhydride, N-vinylcarbazole.

The urethane bond-containing poly (meth) acrylate (B) is used in an amount of 0.1 parts by weight based on 100 parts by weight of all monomers.
It is preferable to copolymerize 10 to 10 parts by weight, more preferably 0.5 to 5 parts by weight. If the amount is less than 0.1 part by weight, the effect of crosslinking is insufficient and the object of the present invention cannot be achieved. If the amount is more than 10 parts by weight, the amount of crosslinking becomes excessive and high initial performance cannot be obtained. The polyfluoroalkyl group-containing (meth) acrylate (A) is preferably copolymerized in an amount of 40 parts by weight or more, more preferably 55 parts by weight or more, based on 100 parts by weight of all the monomers. If this ratio is small, it becomes difficult to exert sufficient water / oil repellency.

For the same reason, the amount of the copolymerizable monomer is preferably 55 parts by weight or less, more preferably 45 parts by weight or less, based on 100 parts by weight of all the monomers. When copolymerizing a copolymerizable monomer, the lower limit is not particularly limited, but an effective amount (for example, 5 parts by weight based on 100 parts by weight of all monomers) is suitable according to the purpose of use.

(C) in the present invention is a copolymer obtained by copolymerizing the above-mentioned (A) and (B), or (A) and (B) and a copolymerizable monomer. In order to obtain this copolymer, various polymerization reaction methods and conditions can be arbitrarily selected, and for example, various polymerization methods such as bulk polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, and photopolymerization are adopted. be able to. Specifically, for example, in the case of emulsion polymerization, a method of emulsifying a mixture of monomers in water in the presence of a surfactant or the like and polymerizing it with stirring can be adopted. As the polymerization initiation source, various polymerization initiators such as organic acid peroxides, azo compounds and persulfates, and ionizing radiation such as γ-rays can be used. As the emulsifier, various anionic, cationic or nonionic surfactants can be used.

For solution polymerization, for example, the monomer is dissolved in an appropriate organic solvent and the polymerization is initiated by the action of a polymerization initiation source (which is soluble in the organic solvent used). Solvents suitable for solution polymerization include chlorine-based and fluorine-based solvents such as trichlorotrifluoroethane, tetrachlorodifluoroethane, and methylchloroform, and further methyl isobutyl ketone, methyl ethyl ketone, butyl acetate, ethyl acetate and the like can be used.

The water / oil repellent composition of the present invention can be obtained by incorporating the blocked polyisocyanate compound (D) into the obtained copolymer (C). Further, since the blocked polyisocyanate compound (D) is a non-copolymerizable compound, the (D) may be present in the polymerization system during the above polymerization. The amount of the blocked polyisocyanate compound (D) with respect to the copolymer (C) is not particularly limited, but the intended purpose can be achieved even with a small amount. The amount thereof is preferably 0.1% by weight or more, and particularly preferably 1% by weight or more based on the copolymer (C). The upper limit is not particularly limited, but 1
About 0% by weight is suitable.

(D) in the present invention is a blocked polyisocyanate compound, which is a compound having one or more, preferably two or more, isocyanate groups blocked with a blocking agent. This (D) is a blocking agent for the isocyanate group in the above-mentioned polyisocyanate compound or a modified product thereof, or an isocyanate group-containing prepolymer obtained by reacting an excess amount thereof with a polyol. Obtained by blocking.

As the polyisocyanate compound, specifically, the above-mentioned specific compounds, particularly diisocyanate compounds are preferable. As the blocking agent, a known blocking agent capable of blocking an isocyanate group can be used. Preferable specific examples include oximes, phenols, β-diketones, malonic acid esters, lactams, and the like. Alkyl ketoxime is particularly preferable from the viewpoint of decomposition temperature.

This (D) is preferably a compound represented by the following general formula (2), which is a diisocyanate compound blocked with an alkyl ketoxime.

[R ⁵ R ⁴ C = NO-CO-NH-] ₂ -R ³ (2) where R ³ is a residue obtained by removing an isocyanate group from a diisocyanate compound, R ⁴ and R ⁵ is a lower alkyl group,
Represents.

In the above general formula (2), R ³ represents two isocyanate groups selected from diisocyanate compounds selected from tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. It is preferably a residue excluding. The lower alkyl group as R ⁴ and R ⁵ is an alkyl group having 1 to 4 carbon atoms.

The water / oil repellent composition of the present invention is prepared in an arbitrary form such as an emulsion, a solvent solution and an aerosol according to a conventional method. For example, an aqueous emulsion type composition is prepared by the emulsion polymerization method as described above, and a solvent solution type composition is prepared by solution polymerization.

The water and oil repellent composition of the present invention is applied to an article to be treated by any method depending on the type of the article to be treated and the form of preparation. For example, in the case of an aqueous emulsion or a solvent solution, a method of adhering it to the surface of the object to be treated by a coating method such as dip coating and drying it is adopted. Also,
Curing may be performed if necessary. Further, the water / oil repellent composition of the present invention may contain other additive components. For example, other water repellents, oil repellents, cross-linking agents, insect repellents, flame retardants, antistatic agents, anti-wrinkle agents and the like can be appropriately added and used in combination.

The article that can be treated with the water / oil repellent composition of the present invention is not particularly limited. For example, fiber woven fabrics, fiber knits, leathers, and furs. Textile fibers, as textile fabrics,
Natural animal and plant fibers such as cotton, hemp, wool and silk, polyamide,
Examples thereof include synthetic fibers such as polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene, semi-synthetic fibers such as rayon and acetate, and woven or knitted fabrics of these mixed fibers.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to these Examples.

[0037]

EXAMPLES The water repellency and oil repellency shown in the following examples were evaluated by the following evaluation tests. Water repellency: It is represented by the water repellency number (see Table 1) by the spray method of JIS L-1092. Oil repellency: A few drops (diameter about 4 mm) of the test solution shown in Table 2 were placed on two places on the test cloth, and the state of permeation after 30 seconds was determined (AATCC-TM118-1966).

The following water repellency No. And oil repellency No.
The evaluation results, which are indicated by a + sign, indicate that each evaluation is N
o. It is slightly better than that represented by.

[0039]

[Table 1]

[0040]

[Table 2]

Example 1 In a glass autoclave equipped with a thermocouple type thermometer and an electric stirrer (internal volume 1 liter), 60 parts by weight of perfluoroalkylethyl acrylate (hereinafter referred to as FA) and DMA (a) ) 1.5 parts by weight, BISO (a) 1.5 parts by weight, EHMA 37 parts by weight, polyoxyethylene lauryl ether 5 parts by weight, stearyl trimethyl ammonium chloride 1 part by weight,
Acetone (60 parts by weight), water (175 parts by weight), and an initiator (a) for polymerization (0.5 parts by weight) were added, and nitrogen substitution was carried out for about 20 minutes while stirring. Let it start. Stir at 60 ° C for 15 hours and then cool,
An emulsion having a solid content concentration of 31% by weight was obtained.

The conversion rate of the copolymerization reaction by gas chromatography was 99.0 to 99.8% (based on the polyfluoroalkyl group-containing monomer compound). Further, the yield of the stable emulsion emulsion with respect to all the monomers is 95-
It was 99%.

The abbreviated compounds are as follows. In addition, the raw material compounds used in the following Example 2 and the following and Comparative Examples are also shown below. FA; R _f CH ₂ CH ₂ OCOCH = CH ₂ , the average carbon number of R _f is about 9. DMA (a); Reaction product of 1 molecule of hexamethylene diisocyanate and 2 molecules of 2-hydroxyethyl methacrylate. DMA (b); Reaction product of 1 molecule of diphenylmethane diisocyanate and 2 molecules of 2-hydroxyethyl methacrylate.

BISO (a): Reaction product of 1 molecule of hexamethylene diisocyanate and 2 molecules of methyl ethyl ketoxime. BISO (b); diphenylmethane diisocyanate 1
A reaction product of a molecule and two molecules of methylethylketoxime. BISO (C); reaction product of 1 molecule of a modified isocyanurate ring of hexamethylene diisocyanate and 3 molecules of methyl ethyl ketoxime. Initiator (a); Azobis (dimethylene isobutyramidine), <Wako Pure Chemical Industries, Ltd., trade name "VA-06"
1 ">. Initiator (b); 2,2'-azobis (2-amidinopropane) dihydrochloride, <Wako Pure Chemical Industries, Ltd. product, trade name" V "
-50 ">.

EHMA; 2-ethylhexyl methacrylate. StMA; stearyl acrylate. VC: Vinyl chloride. AIBN; Azobis (isobutyronitrile).

[Example 2] 60 parts by weight of FA, 1.5 parts by weight of DMA (a), and BISO (a) in a glass autoclave (internal volume of 1 liter) equipped with a thermocouple type thermometer and a current type agitator. 1.5 parts by weight, 37 parts by weight of EHMA, 233 parts by weight of 1,1,1-trichloroethane, and A
After adding 3 parts by weight of IBN and performing nitrogen substitution for about 20 minutes while stirring, the temperature was raised to 60 ° C. to start polymerization. 6
Stir for 20 hours at 0 ° C and then cool to a solids concentration of 31
A wt% pale yellow solution was obtained. The conversion rate of the copolymerization reaction by gas chromatography was 99.0 to 99.8% (based on the polyfluoroalkyl group-containing monomer compound).

[Examples 3 and 4] In the same manner as in Example 1, emulsion polymerization was carried out by changing the monomers, the polymerization initiator, the blocked polyisocyanate compound and the like. The combination of raw materials used is shown in Table 3, the polymerization initiator and the polymerization conditions are shown in Table 4,
Show.

[Examples 5 and 6] In the same manner as in Example 2, solution polymerization was carried out by changing the monomers, the polymerization initiator, the blocked polyisocyanate compound and the like. The combination of raw materials used is shown in Table 3, the polymerization initiator and the polymerization conditions are shown in Table 4,
Show.

[Comparative Example 1] Polymerization was carried out in the same manner as in Example 1 except that the blocked polyisocyanate compound was not contained to obtain an emulsion having a solid content concentration of 30% by weight. Table 3 shows combinations of raw materials used, and Table 4 shows polymerization initiators and polymerization conditions.
Is shown in.

[Comparative Example 2] Polymerization was carried out in the same manner as in Example 2 except that the blocked polyisocyanate compound was not contained to obtain a pale yellow solution having a solid content concentration of 30% by weight. The combination of raw materials used is shown in Table 3, the polymerization initiator and the polymerization conditions are shown in Table 4,
Show.

[Comparative Example 3] Polymerization was carried out in the same manner as in Example 1 except that dimethacrylate containing urethane was not used,
An emulsion having a solid content concentration of 30% by weight was obtained. Table 3 shows combinations of raw materials used, and Table 4 shows polymerization initiators and polymerization conditions.
Is shown in.

[Comparative Example 4] Polymerization was carried out in the same manner as in Example 2 except that dimethacrylate containing urethane was not used.
A pale yellow solution having a solid content concentration of 30% by weight was obtained. Table 3 shows combinations of raw materials used, and Table 4 shows polymerization initiators and polymerization conditions.
Is shown in.

[0053]

[Table 3]

[0054]

[Table 4]

The solid content concentration of the emulsion-polymerized emulsion obtained by the above method was adjusted to 20% by weight to prepare a latex stock solution, which was diluted with water (the ratio of the stock solution to water was 1.5% by weight). ) A latex processing solution was prepared.
The water / oil repellency was measured using this latex treatment liquid. On the other hand, the solution obtained by solution polymerization is 1,1,1
-The solid content concentration was adjusted to 20% by weight with trichloroethane to prepare a stock solution, and this stock solution was further diluted with 1,1,1-trichloroethane (the ratio of the stock solution to the solvent was 1.5%).
% By weight) The water / oil repellency performance was measured.

The test was carried out on a nylon taffeta cloth, and the water and oil repellent treatment was carried out as follows. That is, the test cloth was dipped in the latex treatment solution or 1,1,1-trichloroethane solution diluted as described above, and the cloth was squeezed between two rubber rollers to obtain a wet pickup of 30% by weight.
And Then, it is dried at 110 ° C. for 90 seconds and further 1
Heat treatment was performed at 70 ° C. for 60 seconds. Washing durability is JIS L
-0217 103 method was repeated 5 times, and then 10
It was dried at 0 ° C. for 3 minutes and used for the test. The water and oil repellency of the test cloth thus obtained was measured and the results are summarized in Table 5.

[0057]

[Table 5]

[0058]

EFFECTS OF THE INVENTION By blending the blocked polyisocyanate compound (D) with the copolymer (C) having good water / oil repellency, excellent repellency capable of exhibiting high durability which has hitherto been unattainable. A water / oil repellent composition was obtained.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C09K 3/18 102 8318-4H D06M 13/395 15/263

Claims (5)

[Claims] 1. An acrylate or methacrylate (A) containing a polyfluoroalkyl group and a polyacrylate or polymethacrylate (B) having a urethane bond.
A water and oil repellent composition comprising a copolymer (C) obtained by copolymerizing at least two types of monomers containing as essential components, and a blocked polyisocyanate compound (D). 2. A polyacrylate or polymethacrylate (B) having a urethane bond is represented by the following general formula (1):
The water / oil repellent composition according to claim 1, which is a compound represented by: [CH ₂ = C (R ¹ ) -COO-R ² -O-CO-NH-] ₂ R ³ (1) where R ¹ is a hydrogen atom or a methyl group, and R ² is a diol in which the hydroxyl group is removed. And R ³ represents a residue obtained by removing an isocyanate group from a diisocyanate compound. 3. The water / oil repellent composition according to claim 1, which is obtained by polymerizing (A) and (B) in the presence of a blocked polyisocyanate compound (D). 4. The blocked polyisocyanate compound (D) is a compound represented by the following general formula (2):
The water / oil repellent composition according to claim 1 or 3. [R ⁵ R ⁴ C = NO-CO-NH-] ₂ -R ³ (2) However, R ³ is a residue obtained by removing an isocyanate group from a diisocyanate compound, and R ⁴ and R ⁵ are respectively Lower alkyl group,
Represents. 5. The water / oil repellent composition according to claim 1, wherein the copolymer (C) is a copolymer obtained by copolymerizing (A) and (B) with vinyl chloride or stearyl acrylate.