JPH021794A - Water and oil repellent and water and oil repelling composition - Google Patents

Abstract

PURPOSE:To provide the subject composition composed of an ester of a polymeric compound containing plural hydroxyl groups and a compound containing perfluoroalkyl group and carboxyl group and capable of imparting a surface with scratch resistance when applied by coating, spraying, etc. CONSTITUTION:The objective composition solid at normal temperature is an ester of (A) a polymeric compound having >=3 hydroxyl groups, preferably composed of PVA or polyvinyl butyral and usually having a molecular weight of several tens thousand to several hundred thousand and (B) a compound having perfluoroalkyl group and one or more carboxyl groups. The amount of the component B is preferably 0.2-0.9 equivalent of the carboxyl group in the compound based on 1 equivalent of the hydroxyl group of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a water/oil repellent agent that imparts water/oil repellency to various products such as plastics, glass, fibers, etc., and a composition containing the same.

(Prior technology) Plastic molded bodies; Glass products such as mirrors; Textile products such as clothing and umbrellas may require water- and oil-repellent functions, and various water- and oil-repellent agents have been developed. has been done. Most water and oil repellents are fluorine-containing compounds. For example, JP-A-58-192852 and JP-A-58-
Publication No. 152830 discloses a new fluorine-containing monomer for synthesizing a fluorine-containing polymer that can be used as a water/oil repellent agent.

The above-mentioned JP-A-58-192852 discloses a vinyl ester compound having a perfluoroalkyl group in its side chain.

And, in the above-mentioned Japanese Patent Application Laid-open No. 58-152830, δ-
Fluoro-α,β-unsaturated aliphatic compounds are disclosed.

An example of a fluorine-containing polymer that can be used as a water/oil repellent is perfluoroalkylethyl acrylate.

Examples include polymers obtained by copolymerizing perfluoroalkyl methacrylate with various monomers. For example, in JP-A-57-180680.

A polymer is disclosed in which a backbone segment made of a copolymer containing a diene monomer is bonded to a technical segment containing a blocked polyfluoroalkyl group (for example, polyfluoroalkyl acrylate). JP-A-61-2
Publication No. 09286 discloses a copolymer of a polyfluoroalkyl group-containing vinyl monomer and an alkoxysilyl group-containing vinyl monomer. Many various compositions containing such fluorine-containing polymers are also known. for example.

JP-A-58-147483 discloses a composition containing a polyfluoroalkyl group-containing silane compound, a silane coupling agent, and colloidal silica for the purpose of imparting water and oil repellency to a glass surface. ing.

JP-A-58-104978 discloses compositions containing various fluoropolymers, chlorinated solvents, and propellants as aerosol-type water- and oil-repellent compositions intended to be applied to the surface of textile products. Disclosed. In addition, JP-A-5
Publication No. 9-219380 (d) discloses a water- and oil-repellent emulsion containing a (co)polymer containing a fluorine-containing vinyl monomer.

The fluorine-containing polymer obtained by polymerizing the above-mentioned monomer, the above-mentioned water- and oil-repellent polymer, or the above-mentioned composition are all applied to the surface of textile products, glass, various molded objects, etc. by coating or spraying. For example, when imparting water and oil repellency to the surface of plastic molded objects.

If a water/oil repellent agent can be mixed with a plastic material and molded by injection molding or extrusion molding, the above-mentioned coating and spraying steps will be unnecessary, and productivity will be improved. However, all of the above-mentioned water and oil repellents (polymers or compositions) have drawbacks such as poor affinity with plastic materials and bleeding on the surface of the molded product after molding. Furthermore, when the above-mentioned water- and oil-repellent polymers or compositions are applied to the surfaces of various molded objects by coating or spraying, there is a drawback that the resulting coating surface has poor scratch resistance.

(Problem to be solved by the invention) The present invention solves the above-mentioned conventional drawbacks.

Its purpose is to be able to impart water/oil repellency to the surface of objects that require it by means such as coating or spraying.

The object of the present invention is to provide a water/oil repellent that can be mixed with materials such as plastics and melt-molded, and a composition containing the same. Another object of the invention is.

It is an object of the present invention to provide a water- and oil-repellent composition that can provide a surface with excellent scratch resistance when applied to the surface of an object by means such as coating or spraying.

(Means and effects for solving the problems) The water/oil repellent of the present invention is an ester of a polymer compound having at least three hydroxyl groups and a compound having a perfluoroalkyl group and at least one carboxyl group. It becomes.

The water- and oil-repellent composition of the present invention contains the above-mentioned ester and polymer compound.

The water-repellent/oil-repellent composition of the present invention is the above-mentioned ester.

Contains a polymer compound and a solvent.

One of the water and oil repellent compositions of the present invention is the above-mentioned ester.

Contains metal alkoxide and solvent.

The polymer compound having at least three hydroxyl groups (hereinafter referred to as a hydroxyl group-containing polymer compound) used for preparing the ester that is the t9 water/oil repellent of the present invention is not particularly limited, and the polymer compound having at least three hydroxyl groups is not particularly limited. Olefin-based polymers, ester-based polymers, nylon-based polymers, etc., are used.

Polyvinyl alcohol and polyvinyl butyral are preferably used. The molecular weight of these polymer compounds is usually from tens of thousands to hundreds of thousands.

As a compound having a perfluoroalkyl group and at least one carboxyl group (hereinafter referred to as a carboxyl group-containing fluorine compound), the number of carbon atoms (n) in the perfluoroalkyl group (C, F!fi.1) is 4. The above compounds are advantageously used, and compounds in which n is 7 or 8 are particularly preferred. Examples of the above compounds include the following compounds: C,,F=,. +-CHzC1l□-C00
II, C, Fz, l++-Cth-COOH, C,
1Fzll-+-CHzCHzSCHzCHz-COO
II, Cl1Fz□+-CHzSCHzClh-C
OOH, C6Fzn-+-CHzC1l□5C)Iz-
COOII, C,1Fzll-+-(CH□h-CO
OFI, CllF2-, -(CH2)4-COOI
l, CnFz□+-(C1h)s-COOH,C-F
z, l−+−(CHz)i, −COOH.

C, F2-+l-5NIICII□CHz-COOH,
C, Fz. . r-5NHHz-COOH.

C-Fz, 1-+-CHzCHzSC1l (COOH)
zl C, lPz, 1-+-CHzCHzSCHz-C
Il(COOH)2. C, IFg, %-+-CHz
CH(COOH)z, C11h, l-+-CH(COO
H)-C)1. COO11゜These compounds are! Jl
When the metal alkoxide mentioned in the composition is not contained, the reaction is generally carried out so that the amount of carboxyl groups in the compound is 0.2 to 1 equivalent per 1 equivalent of hydroxyl group in the hydroxyl group-containing polymer compound. . When the metal alkoxide described below is contained in the composition, these carboxyl group-containing fluorine compounds are such that the carboxyl group in the compound is 0.0.
It is preferably contained in an amount of 2 to 0.6 g equivalent.

If the amount of the hydroxyl group-containing polymer compound is too large, the surface energy (critical surface tension) will increase due to the influence of the hydroxyl groups.
a Water and oil repellency decreases. On the other hand, if the amount of the hydroxyl group-containing polymer compound is extremely small, the adhesion to the base material will be poor when the salt water/oil adding composition is applied.

The type of metal alkoxide is also not particularly limited.

Metal alkoxides for hard cords such as silicone-based, aluminum-based, titanium-based, and zirconium-based metal alkoxides are preferably used. It includes St (OEt) a.

Si(OMe)n, 5i(iso-OPr)n,
5i(L-OBu)4+ 8I (OMe)s+8to(OEt)z, At(iso-OPr)s,
Al(t-OBu)++ Ti(OMe)4゜Ti(
OEυ41 Ti(OPr)4. Ti(OBu)4.
Zr(OMe)a.

Zr(OEt)4. Zr(OPr)4. Zr(OBu
)4. Ca(OMe)z.

Ca(OEt)z, Ca(OPr)2. Ca(O
Bu)z etc. The amount of these metal alkoxides is 0.0% per equivalent of hydroxyl group in the above-mentioned hydroxyl group-containing polymer compound.
It is preferably contained in the composition in an amount of 1 to 0.5 equivalents.

The polymer compound contained in the composition may be a thermoplastic resin or a thermosetting resin.

Examples of the thermoplastic resin include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, polycarbonate, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and the like.

Thermosetting resins include epoxy resin, urethane resin,
Examples include melamine resin, phenol resin, silicone resin, imide resin, allyl resin, and unsaturated polyester.

The solvent contained in the composition is mainly contained in one composition when the composition is used as a salt water/oil repellent material for painting or spraying, and is curable resins). Such a solvent is not particularly limited as long as it can dissolve the ester or polymer compound. As the solvent, ethyl acetate, propyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, ethylbenzene, xylene, cyclohexane, etc. are used. or,
A solvent containing a mixture of these and an alcohol such as methanol, ethanol, propatool, etc. is used.

The ester that is solid at room temperature and contained in the salt water/oil repellent composition of the present invention can be obtained by reacting the hydroxyl group-containing polymer compound and the carboxyl group-containing fluorine compound in a conventional manner. for example.

These compounds can be obtained by dissolving these compounds in a suitable solvent having a boiling point of 60°C or higher, adding a catalyst, and heating at 60 to 100°C for 6 to 12 hours. As the solvent, the above-mentioned solvents are preferably used. The above-mentioned catalysts include acids commonly used in esterification reactions.

For example, inorganic acids such as concentrated sulfuric acid and concentrated hydrochloric acid; or organic acids such as trifluoroacetic acid and difluoroacetic acid are used.

The above reaction temperature and reaction time vary depending on the type of hydroxyl group-containing polymer compound and carboxyl group-containing fluorine compound used, so conditions should be selected that provide high esterification efficiency and do not cause decomposition or side reactions of raw materials and products. , is set appropriately. Since the obtained ester is solid at room temperature, 1 For example, when it is applied to the surface of a molded object as a water repellent or oil repellent, or when it is mixed with a plastic material and molded, it stably exists on the surface of the molded object. do.

The above ester can be applied as it is, for example, to the surface of a glass or plastic molded body by a method such as casting, and used as a water/oil repellent. Furthermore, a water/oil repellent composition containing the above water/oil repellent agent and a polymer compound can be prepared. Such a composition includes, for example, the above-mentioned polymer compound (thermoplastic resin or uncured thermosetting resin) and the above-mentioned ester. When this composition is heated and melted and molded by extrusion molding, injection molding, etc., it becomes water repellent! 8. A plastic molded article having oiliness is obtained. In a composition containing a polymer compound, the ester to be used is appropriately selected depending on the type of the polymer compound and its affinity. In the above composition, the ester has a C-h-11 content of 1% by weight or more.

It is preferably contained in a proportion of 1.2 to 20% by weight.

In case of masterbatch composition 1 usually + Cr + F2
The r++1 content is contained at a ratio of 20 to 80%.

Another water/oil repellent composition of the present invention contains the above-mentioned ester, polymer compound, and solvent. Such a composition is
It is used for the purpose of imparting water- and oil-repellent waves to the surfaces of various molded objects and textile products such as glass, plastics, metals, and ceramics by means of coating, casting, spraying, etc. The type of solvent is appropriately selected depending on the type of ester and polymer compound contained.

For example, a coating composition is prepared that includes a thermoplastic resin or an uncured thermosetting resin and a solvent capable of dissolving it. The blending ratio of the polymer compound and ester is based on the composition containing the above-mentioned polymer compound and ester, and an appropriate amount of solvent is blended therein depending on the purpose.

Furthermore, the water- and oil-repellent composition of the present invention comprises the above-mentioned ester,
Contains metal alkoxide and solvent.

Such a composition is used as a water- and oil-repellent composition for coating or casting, similar to the composition containing the ester, polymer compound, and solvent described above. The solvent used here is an alcoholic solvent or a mixture of an alcoholic solvent and the above-mentioned organic solvent. The metal alkoxide reacts with the remaining hydroxyl groups of the ester to form an ester. The metal alkoxide may be a monomer, but in order to improve the scratch resistance, it is preferable to use a partially hydrolyzed multimer having a molecular weight of about 1000 to 5000. The coating film obtained when one composition is applied contains a reaction product between a metal alkoxide and an ester, and/or a reaction product between a polymer and an ester that is a metal alkoxide hydrolyzate. Excellent scratch resistance. The larger the molecular weight of the polymer, the easier the handling of the 9 composition, and the better the scratch resistance of the resulting coating film.

The ester used in the present invention has a perfluoroalkyl group that has excellent water and oil repellency, so it has excellent water and oil repellency and is excellent in compatibility with various resins. The composition of the present invention containing the ester and the polymer compound can be molded by, for example, extrusion molding or injection molding.

The obtained molded product has excellent water and oil repellency.

Furthermore, the composition of the present invention containing a solvent is used as a water- and oil-repellent composition for painting, and the resulting coating film has excellent water- and oil-repellency. It also has excellent adhesion between the coating film and the surface being coated. Furthermore, since a reaction product between the metal alkoxide and the ester is present in the coating film obtained when the composition of the present invention containing the above-mentioned metal alkoxide is applied to the surface of a molded article, the coating film has water and oil repellency. In addition, it has excellent scratch resistance.

(Example) The invention will be explained below with reference to examples.

Fusenukijo Nijo (^) Ester's 1-water product: Polyvinyl alcohol (ri-
7L/manufactured by PVA-117) 4.5g (saponification degree 98.5%) and CeF+v-CIIzCHz-Co
ol 38. Og (0.08 mol).

It was dissolved in a mixed solvent of 200ml of toluene and 50ml of methanol.To this was added 0.98g of concentrated sulfuric acid.
01 mol) and reacted under reflux at 85°C for 10 hours. This reaction solution was poured into water, and a white precipitate was collected. This was thoroughly washed with toluene to obtain 24.5 g of a white product (half ester). As a result of elemental analysis of this produced proboscis, the ratio of C:H was 15.3:1.0, and the esterification rate was 43%.

(B) Performance evaluation of ester = Dissolve the ester obtained in (8) in toluene and cast to a thickness of 3
A film of 0 μm was formed. Water and n-octane droplets were brought into contact with the surface, respectively.

The contact angle was measured using a contact angle measuring device CA-D (manufactured by Kyowa Interface Science Co., Ltd.). Furthermore, the pencil hardness of the coated surface was measured in accordance with JIS K-5400. The results are shown in Table 1.

(C) Performance evaluation of ester-containing compositions: Various base resins [
Polystyrene (manufactured by Denki Kagaku Kogyo Co., Ltd., Denka Styrol M
W-1), polymethyl methacrylate (manufactured by Kyowa Gas Chemical Co., Ltd., Parapet GF), polycarbonate (manufactured by Teijin Kasei Co., Ltd., Panrai 1-L-1250)], (
The ester (half ester) obtained in section 8) was blended at a ratio of 5% by weight, and this was dissolved in toluene. This solution was cast and dried to form a film with a thickness of 30 μm. Water and n-octane droplets were brought into contact with the surface, and the contact angle was measured using the same measuring device as in this example (Δ). The results are shown in Table 2.

4 CJ+ as a carboxyl group-containing fluorine compound? -CI
IzCHzSCtlzCHz-COOII 42.8
g (0.08 mol) was used.

It is the same as Example 1-1 except that the reaction temperature was 80°C. The yield, esterification rate, performance, etc. of the obtained ester are shown in Tables 1 and 2. Examples 1-3 to 1 described below
-6 results are also shown in Tables 1 and 2.

nhua↓C8F+ as a fluorine compound containing a carboxyl group? -C
HtCHzSCFlt-COOH41,7g (0,0
The procedure was the same as in Example 1-1 except that 8 mol) was used and the reaction temperature was 80°C.

CaFl? CH
zCHzSCH-(COON)t 22.6g (0,
04 mol) was used.

The procedure was the same as in Example 1-1 except that the reaction temperature was 80''C.

LL Biped Polyvinyl Butyral (B11-3 manufactured by Block Chemical ■) 6.
0g (degree of butyralization 72%) in methanol LooIn
CeF+ was dissolved in Il and stirred at 80°C under reflux.
, -CIl□CUtcoO) 123.75 g (0,
05 mol) toluene solution and concentrated sulfuric acid 0.5 g (0,
005 mol) was added dropwise, and after one drop, the mixture was reacted for 8 hours. The reaction solution was poured into toluene, and the precipitated white reaction product (
Half ester) 10.1g was obtained. Using this ester, performance evaluation was performed in the same manner as in Example 1-1.

CsF+1-C as a fluorine compound containing a carboxyl group
Il□CH25C1I□C1h-COOH26,75g
It is the same as Example 1-5 except that (0.05 mol) was used.

Example 1-1 (C) The same base resin as used in Section (C) was blended with polyvinyl alcohol (PVA) at a ratio of 5% by weight. Form a film according to
The contact angles of water and n-octane droplets were measured, respectively. The results are shown in Table 2.

Kitamoto J [L21 Example 1-1 Only the resin used as the base material in section (C) was cast according to Example 1-1 (C) to form a coating film, and water and The contact angle of octane droplets was measured. The results are shown in Table 2.

Only the polyvinyl alcohol used in Example 1-5 and the polyvinyl butyral used in Example 1-6 were used in Example 1.
-1 A film was formed by casting according to Section (C), and the contact angles of water and n-octane droplets were measured. The results are shown in Table 3.

(Margin below) Table 3 Example 1-1 The ester obtained in section (A) was dissolved in a hexafluorometa-xylene-methanol mixed solvent at a ratio of 5% by weight, and the solid content was adjusted to 20% by weight. An alkoxysilane (Cerasol, manufactured by Colcoat) solution was added to the mixture and stirred thoroughly.

This was cast onto a glass substrate, dried at room temperature, and then cured at 80°C for 2 hours. Water and n-octane droplets were brought into contact with the surface of the obtained film, and the contact angle was measured using the same measuring device as in Example 1-1. Furthermore, the pencil hardness of the coating surface was determined according to JIS K-5400.
Measured according to the method. The results are shown in Table 4. The results of Examples 2-2 to 2-8, which will be described later, are also shown in Table 4.

The procedure was the same as in Example 2-1 except that the ester obtained in Example 1-2 was used.

The procedure was the same as in Example 2-1 except that the amount of penta-di-primary alkoxysilane was added so that the solid content was 10% by weight.

The procedure was the same as in Example 2-2, except that the amount of L1 soil alkoxysilane was added to give a solid content of 10%.

Example 2-1 Same as Example 2-1 except that the ester obtained in Example 1-3 was used.

The procedure was the same as in Example 2-1 except that the ester obtained in Example 1-4 was used.

1/21 The same as Example 2-1 except that the ester obtained in Example 1-5 was used.

Example 1 Example 1 Same as Example 2-1 except that the ester obtained in Example 1-6 was used.

(Hereinafter in the margin) (Effects of the Invention) According to the present invention, it is possible to impart water repellency and oil repellency to the surface of objects that require it by means such as coating and spraying, and Provided are water and oil repellents that can be melt-molded by being mixed with materials such as, and compositions containing the same. In particular, with the composition of the invention containing a metal alkoxide,
The film obtained by coating has excellent scratch resistance.

The water/oil repellent of the present invention and the composition containing the same are:
Various molded objects such as glass and plastic.

It can impart excellent water and oil repellency and stain prevention properties to textile products.

that's all

Claims (1)

[Claims] 1. A polymer compound having at least three hydroxyl groups;
A water/oil repellent agent comprising an ester with a compound having a perfluoroalkyl group and at least one carboxyl group, which is solid at room temperature. 2. A water- and oil-repellent composition containing the ester according to claim 1 and a polymer compound. 3. A water- and oil-repellent composition containing the ester according to claim 1, a polymer compound, and a solvent. 4. A water- and oil-repellent composition containing the ester according to claim 1, a metal alkoxide, and a solvent.