WO2019069503A1 - Antifouling composition, container, sanitary member, kitchen member, home appliance member, and stationery member - Google Patents

Abstract

The present invention pertains to an antifouling composition, a container, a sanitary member, a kitchen member, a home appliance member, and a stationery member. This antifouling composition contains (A) at least one resin selected from propylene resins, styrene-based resins, and polyphenylene ether resins, and (B) a polyester-modified or alkyl-modified silicone compound which is solid at 25°C.

Description

Antifouling composition, container, sanitary member, kitchen member, home appliance member and stationery member

The present invention relates to an antifouling composition, a container, a sanitary member, a kitchen member, a household electric appliance member and a stationery member.

Conventional containers such as food containers and sanitary members such as toilet members are susceptible to stains, and therefore containers and members that are resistant to such stains and have excellent antifouling properties are required.

To meet such requirements, Patent Document 1 discloses a resin composition containing a polyolefin resin, a high molecular weight silicone resin, a higher fatty acid amide, and a low molecular weight silicone resin as a component which oozes from the inside of a molded article to the surface with time. It is described that the molded article which is excellent in antifouling property can be obtained by using.
Patent Document 2 describes a composition comprising a specific copolymer and a modified polyorganosiloxane containing at least one reactive group selected from an epoxy group, a carboxyl group and an acid anhydride group. Document 3 describes a resin composition comprising a rubber-modified styrenic resin and a polyorganosiloxane having a viscosity of 500 to 100,000 cSt.

Patent No. 3359723 gazette Japanese Patent Application Laid-Open No. 10-316833 Patent No. 2688619 gazette

As a result of intensive studies by the present inventors, molded articles formed from the resin compositions described in Patent Documents 1 to 3 are not sufficiently antifouling, and there is room for improvement, particularly in terms of antifouling to oil components. The

One embodiment of the present invention provides a composition capable of easily forming a film or a molded article which is particularly excellent in the antifouling property to oil.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining that the present inventor should solve the said subject, according to the following composition, it discovers that the said subject can be solved and came to complete this invention.
The structural example of this invention is as follows.

[1] Containing at least one resin (A) selected from a propylene resin, a styrene resin and a polyphenylene ether resin, and a polyester-modified or alkyl-modified silicone compound (B) which is solid at 25 ° C. , Antifouling composition.
[2] The antifouling composition according to [1], wherein the resin (A) is a styrene resin, and the silicone compound (B) is a polyester-modified silicone compound which is solid at 25 ° C.

[3] The antifouling composition according to [1] or [2], wherein the silicone compound (B) is a compound represented by the following formula (I):

[In the formula (I),
R is, independently of one another, a hydrocarbon group having 1 to 12 carbon atoms,
R ¹ and R ² are, independently of each other, a polyester group, a hydrocarbon group having 1 to 36 carbon atoms, or a group in which a part of the hydrocarbon group is substituted with an oxygen atom,
n, m and p are each independently 0 to 58,
N = n + m + p + 2 is 10 to 75,
At least one of all R ¹ and R ² is a polyester group or an alkyl group having 12 to 36 carbon atoms. ]

[4] The antifouling composition according to [3], wherein the polyester group is a group represented by the following formula (II).
-R ^q- (R ^r ) _z H (II)
[In the formula (II), R ^q is a group represented by — (CH ₂ ) _x —O— (x is 2 to 10,
R ^r is a group represented by —C (= O) — (CH ₂ ) _y —O— (y is 2 to 10),
z is 3-30. ]

[5] The antifouling composition according to [3] or [4], wherein at least one of R ¹ and R ² is a polyester group.

[6] Any of the above [1] to [5], wherein the content of the silicone compound (B) is 0.1 to 30% by weight with respect to the total 100% by weight of the resin (A) and the compound (B) The antifouling composition according to any one of the above.

[7] The antifouling composition according to any one of [1] to [6], which is substantially free of silicone oil.
[8] pigments, dyes, light stabilizers, UV absorbers, antibacterial agents, modifiers, plasticizers, nucleating agents, heavy metal deactivators, stabilizing aids, antistatic agents, conductive agents, flame retardants, The antifouling composition according to any one of [1] to [7], which contains one or more additives selected from a heat stabilizer, an antioxidant, a lubricant, an inorganic filler, a crosslinkable polymer, and a fiber reinforcing agent. object.
[9] The antifouling composition according to [8], wherein the additive is a hydrophobized additive.

[10] A container obtained by using the antifouling composition according to any one of [1] to [9], a sanitary member, a kitchen member, a household electric appliance member and a stationery member.

According to one embodiment of the present invention, it is possible to easily form a film or a molded article which is excellent in the antifouling property to oil. In particular, according to one embodiment of the present invention, a film or a molded article which is excellent in stain resistance over a long period and is lightweight and excellent in durability while maintaining or improving the physical properties of the resin, specifically, A container such as a food container, a toilet member, a sanitary member such as a bathroom member, a kitchen member, a home appliance member and a stationery member can be easily formed at low cost.
Furthermore, according to one embodiment of the present invention, it is possible to form a film or a molded article having excellent antifouling properties over a long period of time while having the effect of an additive.

FIG. 1 shows the FT-IR spectrum of the composition obtained in Example 3. FIG. 2 shows an FT-IR spectrum of the composition obtained in Comparative Example 1.

«Antifouling composition»
The antifouling composition according to an embodiment of the present invention (hereinafter also referred to as "the present composition") is at least one resin (A) selected from propylene resins, styrene resins and polyphenylene ether resins. And a polyester-modified or alkyl-modified silicone compound (B) which is solid at 25 ° C.

In this composition, a combination of a propylene-based resin and an alkyl-modified silicone compound, a styrene-based resin and / or a polyphenylene ether-based resin and a polyester-modified silicone compound, as a combination of the resin (A) and the silicone compound (B). A combination is preferable, a combination of a styrene resin or polyphenylene ether resin and a polyester modified silicone compound is more preferable, a combination of a styrene resin and a polyester modified silicone compound is more preferable, and a combination of an ABS resin and a polyester modified silicone compound is more preferable. Particularly preferred.
When the resin (A) and the compound (B) are in the combination, the compatibility thereof becomes better, so that the compound (B) becomes more dispersed in the resin (A), and the compound (B) Even if a small amount is used, it is possible to easily form a film or a molded article excellent in antifouling property with respect to oil over a long period at low cost, and the film or molded article can be used as a container such as a food container or a toilet member And sanitary members such as bathroom members, kitchen members, household appliance members and stationery members.

The composition may be a composition for forming a film, a molded body or the like (hereinafter also referred to as “molding composition”), or may be a so-called master batch.
The masterbatch generally refers to pellets containing solid components other than resin in a high concentration in a base resin such as a propylene resin, a styrene resin, and a polyphenylene ether resin. Although various resin can be used as base resin, it is preferable to use said resin (A) as base resin in one Embodiment of this invention. The content of solid components in the masterbatch is usually 20 to 70% by weight, preferably 30 to 60% by weight.

The masterbatch is usually diluted by a component containing the same resin as the base resin (hereinafter, the component for diluting the masterbatch is also referred to as a "dilution component"), specifically, the weight of the masterbatch It is diluted by the dilution component in such an amount that the ratio of the weight of the dilution component to the weight of the dilution component (weight of master batch: weight of dilution component) is preferably 1: 1 to 10, more preferably 1: 1 to 5, particularly preferably The following components are each diluted with a dilution component to have the following contents, and are used as a composition when forming a film, a molded article, or the like.
The following descriptions of the content are preferable ranges for the molding composition.

<Resin (A)>
The composition comprises at least one resin (A) selected from the group consisting of propylene resins, styrene resins and polyphenylene ether resins.
The resin (A) contained in the present composition may be one kind or two or more kinds.

The content of the resin (A) in the present composition may be appropriately selected according to the desired application, but preferably 70 to 99.9 based on 100% by weight in total of the resin (A) and the compound (B). % By weight, more preferably 80 to 99% by weight, still more preferably 85 to 99% by weight, particularly preferably 90 to 98% by weight.
When the content of the resin (A) is in the above range, a composition excellent in processability and moldability is obtained, the characteristics of the resin are sufficiently exhibited, and films and molded articles excellent in long-term antifouling properties are easily obtained. You can get it.

[Propylene resin]
The propylene-based resin is not particularly limited, and may be any of a propylene homopolymer, block copolymer and random copolymer, but the rigidity and heat resistance of a film or a molded product obtained from the present composition, etc. From the viewpoint of impact resistance and the like of films and molded articles obtained from the present composition, block copolymers are preferable.
The propylene-based resin may be used alone or in combination of two or more.

The copolymer is obtained by copolymerizing propylene and a comonomer copolymerizable with propylene, and examples of the comonomer include olefins such as ethylene, butene, pentene, hexene and octene, and the like, and preferable. Is ethylene or 1-butene.
Two or more of these comonomers may be used.
The amount of the comonomer used is usually 30% by weight or less, preferably 20% by weight or less, based on 100% by weight of all the monomers used for the synthesis of the copolymer.

The propylene-based resin includes polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, propylene-butene copolymer, Other polymers such as propylene-hexene copolymer, propylene-octene copolymer, butene-hexene copolymer, butene-octene copolymer, alpha-olefin copolymer such as hexene-octene copolymer May be included.

The propylene-based resin may be obtained by synthesis according to a conventionally known method, or may be a commercially available product such as Prime Polymer Co., Ltd., Nippon Polypro Co., Ltd., Sumitomo Chemical Co., Ltd. or Sun Aroma Co., Ltd. Good.

The melt flow rate (MFR) of the propylene-based resin measured at a temperature of 230 ° C. and a load of 2.16 kgf based on JIS K 7210 provides a composition having excellent processability and moldability, and the antifouling effect is enhanced. The amount is preferably 0.3 to 5 g / 10 minutes, more preferably 0.5 to 3 g / 10 minutes, from the viewpoint that the obtained film or sheet can be easily obtained. In addition, a composition having excellent processability and moldability can be obtained, and a molded article such as an injection molded article having an enhanced antifouling effect can be easily obtained, and preferably 5 to 100 g / 10 min. More preferably, it is 10 to 60 g / 10 min.

The Izod impact strength (23 ° C.) of the propylene-based resin measured according to ASTM-D256 is preferably from the viewpoint of easily obtaining molded articles such as injection molded articles having excellent impact resistance. It is 2 to 20 kJ / m ² , more preferably 5 to 20 kJ / m ² .

The flexural modulus of the propylene-based resin measured according to ASTM-D 790 is preferably 1000 to 3000 MPa from the viewpoint that molded articles such as injection molded articles having excellent mechanical strength can be easily obtained. .

[Styrenic resin]
The styrene-based resin is not particularly limited, but is a resin other than a propylene-based resin and a polyphenylene ether-based resin.
The styrenic resin can be obtained by polymerizing a raw material containing an aromatic vinyl monomer. In particular, an aromatic vinyl monomer is polymerized in the presence of a dissolved rubbery polymer, or a copolymer of an aromatic vinyl monomer and a vinyl monomer copolymerizable with the monomer is copolymerized. It is preferable that it is a resin obtained by polymerizing.
The polymerization method is not particularly limited, and conventionally used methods, for example, multistage polymerization methods such as emulsion polymerization method, bulk polymerization method, solution polymerization method, suspension polymerization method, bulk-suspension two-stage polymerization method, etc. be able to.
The styrene resin may be used alone or in combination of two or more.

Examples of the aromatic vinyl monomer include α-alkyl substituted styrenes such as styrene, α-methylstyrene, α-ethylstyrene, α-methyl-p-methylstyrene, o-methylstyrene, m-methylstyrene, nuclear alkyl substituted styrene such as p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, o-t-butylstyrene, p-t-butylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, Nuclear halogenated styrene such as p-bromostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene, tribromostyrene, tetrachlorostyrene, tetrabromostyrene, 2-methyl-4-chlorostyrene, p-hydroxystyrene, o-methoxystyrene And vinyl naphthalene. Among these, in particular styrene and α- methyl styrene. These aromatic vinyl monomers may be used alone or in combination of two or more.

Examples of the vinyl-based monomer copolymerizable with the aromatic vinyl monomer include vinyl cyanide-based monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, maleonitrile, α-chloroacrylonitrile, etc. Maleimide monomers such as maleimide, N-methyl maleimide, N-phenyl maleimide, etc., unsaturated carboxylic acids such as acrylic acid, methacrylic acid, phthalic acid, itaconic acid, maleic anhydride, itaconic anhydride and anhydrides thereof, And unsaturated carboxylic acid esters or amides such as methyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid amide and the like. Among these, vinyl cyanide-based monomers, in particular acrylonitrile, are preferred in that films and molded articles having excellent chemical resistance can be easily obtained. These vinyl monomers may be used alone or in combination of two or more.

Examples of the rubbery polymer include cis-type, trans-type, low vinyl-type polybutadiene obtained by emulsion polymerization or solution polymerization, and butadiene-type such as random type or block-type obtained by emulsion polymerization or solution polymerization Examples thereof include styrene copolymer rubber, natural rubber, polyisobutylene rubber, styrene-isoprene copolymer rubber, butyl rubber, ethylene-propylene copolymer rubber, and graft copolymers of these rubbers and styrene. Among these, polybutadiene and butadiene-styrene copolymer rubber are preferable. These rubbery polymers may be used alone or in combination of two or more.

The styrenic resin comprises 70 to 96 wt% of the combination of the aromatic vinyl monomer and a vinyl monomer copolymerizable with the monomer, and 4 to 30 wt% of the rubbery polymer in a dissolved state. It is preferable that it is resin which superposed | polymerized the mixture containing%, and it is more preferable to contain the graft polymer which graft-polymerized a part of said monomer to this rubbery polymer. When the amount of the rubbery polymer is less than 4% by weight, sufficient impact resistance may not be obtained, and when it exceeds 30% by weight, the rigidity may be reduced.

Typical examples of the styrene-based resin include GPPS resin (styrene polymer), HIPS resin (styrene-butadiene copolymer), AS resin (acrylonitrile-styrene copolymer), ABS resin (acrylonitrile-butadiene-styrene) Copolymer), MS resin (methyl methacrylate-styrene copolymer), AAS resin (acrylonitrile-acryl-styrene copolymer), AES resin (acrylonitrile-ethylene propylene-styrene copolymer), MBS resin (methyl methacrylate- Butadiene-styrene copolymer) and the like. Among these, as a styrene resin, GPPS, HIPS, AS, and an ABS resin are preferable from the point of being excellent by compatibility with a silicone compound (B).

The styrene-based resin may be obtained by synthesis according to a conventionally known method, such as Toyo Styrene Co., Ltd., PS Japan Co., Ltd., DIC Co., Ltd., Denka Co., Ltd., Techno Polymer Co., Ltd., Toray Co., Ltd. Commercial products such as Asahi Kasei Co., Ltd. may be used.

The melt flow rate (MFR) of the styrene resin measured at a temperature of 220 ° C. and a load of 10 kgf based on JIS K 7210 gave a composition excellent in processability and moldability, and the antifouling effect was enhanced. The amount is preferably 0.3 to 5 g / 10 minutes, and more preferably 0.5 to 3 g / 10 minutes, from the viewpoint that a film, a sheet or the like can be easily obtained. In addition, a composition having excellent processability and moldability can be obtained, and a molded article such as an injection molded article having an enhanced antifouling effect can be easily obtained, and preferably 5 to 100 g / 10 min. More preferably, it is 10 to 60 g / 10 min.

The Izod impact strength (23 ° C.) of the styrene resin measured according to ASTM-D256 is preferably from the viewpoint of easily obtaining molded articles such as injection molded articles having excellent impact resistance. 5 kJ / m ² or more, more preferably 15 kJ / m ² or more.

The flexural modulus of the styrene resin measured according to ASTM-D 790 is preferably 2000 MPa or more from the viewpoint that molded articles such as injection molded articles having excellent mechanical strength can be easily obtained.

[Polyphenylene ether resin]
The polyphenylene ether-based resin is not particularly limited, and may be an unmodified polyphenylene ether-based resin or a modified polyphenylene ether-based resin, but a modified polyphenylene ether-based resin is preferable from the viewpoint that the effects of the present invention are more exhibited. .
The polyphenylene ether-based resin may be used alone or in combination of two or more.

As said non-modified polyphenylene ether, polyphenylene ether shown by a following formula is preferable.

In the above formula, R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms or a halogen atom.
n is a positive integer representing the degree of polymerization, and is usually 10 to 5,000.

Examples of such polyphenylene ethers are poly-2,6-dimethylphenylene-1,4-ether, poly-2,6-diethylphenylene-1,4-ether and poly-2,6-dichlorophenylene-1. , 4-ether.

The modified polyphenylene ether may be, for example, a modified product obtained by modifying the unmodified polyphenylene ether with a predetermined substituent as described in WO 2014/203511, and the unmodified polyphenylene ether And a polymer alloy of a thermoplastic resin such as a polystyrene resin.

A non-modified polyphenylene ether resin has a high melting point and is difficult to mold alone, so a polymer alloy with a thermoplastic resin such as a polystyrene resin excellent in compatibility with the polyphenylene ether resin is preferable. Moreover, it is preferable that it is a polymer alloy from the point of being able to obtain the antifouling composition which exhibits a predetermined effect easily and inexpensively.

The polymer alloy may be a polymer alloy of unmodified polyphenylene ether and a thermoplastic resin such as polystyrene, or may be a polymer alloy of the polymer alloy and a thermoplastic resin such as a polystyrene resin.

Examples of the polystyrene-based resin include high-impact polystyrene (HIPS) such as styrene homopolymer, styrene-butadiene copolymer, styrene-α-methylstyrene copolymer, styrene- (meth) acrylonitrile copolymer, styrene- Examples thereof include (meth) acrylic acid copolymers and styrene / (meth) acrylic acid ester copolymers. Among these, a styrene homopolymer or a combination of a styrene homopolymer and HIPS is preferable.
The said polystyrene resin may be used individually by 1 type, and may use 2 or more types.

The amount of the polystyrene resin used is usually 20 to 1000 parts by weight, preferably 50 to 500 parts by weight, per 100 parts by weight of the unmodified polyphenylene ether resin.
When the amount of the polystyrene resin used is in the above range, the characteristics of the polystyrene resin can be imparted while maintaining the excellent characteristics of the polyphenylene ether resin.

The polyphenylene ether-based resin may be obtained by synthesis using a conventionally known method, or a commercially available product such as Asahi Kasei Corp., Mitsubishi Engineering Plastics Corp. or SABIC Co., Ltd. may be used.

The melt flow rate (MFR) of the polyphenylene ether resin measured at a temperature of 300 ° C. and a load of 2.16 kgf based on JIS K 7210 gives a composition excellent in processability and moldability, and has an antifouling effect The amount is preferably 0.3 to 5 g / 10 minutes, more preferably 0.5 to 3 g / 10 minutes, from the viewpoint of easily obtaining an enhanced film, sheet or the like. In addition, a composition having excellent processability and moldability can be obtained, and a molded article such as an injection molded article having an enhanced antifouling effect can be easily obtained, and preferably 5 to 50 g / 10 min. More preferably, it is 10 to 30 g / 10 minutes.

The Izod impact strength (23 ° C.) of the polyphenylene ether resin measured according to ASTM-D256 is preferable from the viewpoint that a molded article such as an injection molded article excellent in impact resistance can be easily obtained. it is 5 kJ / m ² or more, more preferably 15 kJ / m ² or more.

The flexural modulus of the polyphenylene ether resin measured according to ASTM-D 790 is preferably 2000 MPa or more from the viewpoint that molded articles such as injection molded articles excellent in mechanical strength can be easily obtained. .

<Polyester-modified or alkyl-modified silicone compound (B) which is solid at 25 ° C.>
The polyester-modified or alkyl-modified silicone compound (B) is not particularly limited as long as it is a solid at 25 ° C. and is a compound other than the following silicone oil. The alkyl-modified silicone compound is a compound having an alkyl group having 12 to 36 carbon atoms.
By using the silicone compound (B), it is possible to easily form a film or a molded article which is excellent in the antifouling property to oil and which is excellent over a long period of time. In particular, the silicone compound (B) is not a component that bleeds out from a film or a molded product, and is excellent in compatibility with the resin (A), so the compound (B) becomes more dispersed in the resin (A). Even if the compound (B) is used in a small amount, it is possible to easily form a film or a molded article having excellent antifouling properties over a long period with respect to the oil component at low cost.
The silicone compounds (B) may be used alone or in combination of two or more.

The silicone compound (B) is not particularly limited, but a film or a molded article which is excellent in compatibility with the resin (A) and stable can be easily obtained. Polyester-modified silicone compounds are preferred from the viewpoints of being excellent in scratch resistance, chemical resistance, impact resistance, surface smoothness, and easily obtaining a film or molded article in which outgassing is less likely to occur.
In addition, since the polyester-modified silicone compound is less likely to bleed out from the surface of the film or the molded product, a film or a molded product having excellent antifouling properties can be easily obtained over a long period of time.

The silicone compound (B) is not particularly limited, but from the viewpoint of being able to easily form a film or a molded article which is excellent in compatibility with the resin (A) and is more excellent in antifouling property to oil, etc. It is preferable that it is a compound represented by Formula (I).

In formula (I),
R's are each independently a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrocarbon group having 1 to 11 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group. More preferably, it is an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.
R ¹ and R ² are each independently a polyester group, a hydrocarbon group having 1 to 36 carbon atoms, or a group in which a part of the hydrocarbon group is substituted with an oxygen atom.
n, m and p are each independently 0 to 58 and p is preferably 0.
N = n + m + p + 2 is 10 to 75, preferably 15 to 50.
At least one of all R ¹ and R ² is a polyester group or an alkyl group having 12 to 36 carbon atoms.
In the formula (I), the bonding order of repeating units represented by [] _n , [] _m and [] _p is arbitrary.

The polyester group is preferably a repeating unit of an ester structure (hereinafter also referred to as “ester unit”. For example: 3 to 30, more preferably 8 to 25, and further preferably 15 to 25). In particular, a group represented by the following formula (II) is preferable.
-R ^q- (R ^r ) _z H (II)

In the formula (II), R ^q is a group represented by — (CH ₂ ) _x —O— (x is 2 to 10, preferably 3 to 7, more preferably 6),
R ^r is a group represented by —C (= O) — (CH ₂ ) _y —O— (y is 2 to 10, preferably 3 to 8, more preferably 4 or 5),
z is 3 to 30, preferably 8 to 25 and more preferably 15 to 25.

The n, m, p, x, y and z are average values.

It is preferable that at least one of R ¹ and R ² is a polyester group, from the viewpoint that a film or a molded article having more excellent stain resistance to oil can be easily obtained. Compounds in which R ¹ and one or more R ² are polyester groups may also be preferred.
When formula (I) has two or more polyester groups, these polyester groups are preferably the same group.

The hydrocarbon group having 1 to 36 carbon atoms is preferably a hydrocarbon group having 12 to 36 carbon atoms.
Examples of the group in which part of the hydrocarbon group having 1 to 36 carbon atoms is substituted with an oxygen atom include a group containing an ether structure or an ester structure, a group containing a hydroxy group and a carboxy group, and the like.

The carbon number of the alkyl group having 12 to 36 carbon atoms is preferably 20 to 30, and more preferably 24 to 30.

When one or more of R ¹ and / or R ² is a polyester group, N is preferably 10 to 50, more preferably 15 to 45, p is preferably 0, and m is preferably It is 0 to 10, more preferably 1 to 5.

R ² is preferably a polyester group or an alkyl group having 12 to 36 carbon atoms.
When R ² is the above alkyl group, preferably an alkyl group having 30 carbon atoms or an alkyl group having 24 to 28 carbon atoms, R ¹ and R are preferably methyl groups, and N is preferably 40 to 50, More preferably, it is 40 or 50.

If R ¹ and / or R ² is a polyester group, preferably a polyester group having 15 to 25 ester units, R is preferably a methyl group and N is preferably 20 to 45.

As a compound represented by the formula (I), p is 0, R ^q is a hexanol group, R is a methyl group, N, m, R ¹ and R ² are as shown in Table 1 below. Compounds are preferred.

The compounds represented by the formula (I) may be commercially available products, or obtained by reacting the corresponding hydrogen siloxane with an unsaturated hydrocarbon or unsaturated alcohol and then (poly) esterification. It may be obtained by direct reaction of unsaturated polyester and hydrogen siloxane. The reaction can be carried out by hydrosilylation or dehydrogenative hydrosilylation as described in EP1640418. The preparation of the polysiloxane having a polyester group may be referred to, for example, the description of EP 0208734.

The polyester group may be a group formed from the same starting molecule or may be a group formed from different starting molecules, but is preferably a group formed from the same starting molecule.
The polyester group is preferably a group obtained by a ring opening reaction, in particular by poly (esterification) of lactone, and caprolactone or valerolactone, in particular, ε-caprolactone, 3,5,5-trimethylcaprolactone or δ It is more preferred that it is a group obtained by poly (esterification) of -caprolactone and furthermore ε-caprolactone.
As the polyester group, groups having a repeating unit number of ε-caprolactone of preferably 3 to 30, more preferably 8 to 25, and further preferably 15 to 25 can be mentioned.

Since the silicone compound (B) is a solid at 25 ° C., it is not appropriate to define the viscosity at 25 ° C. For example, the viscosity at 25 ° C. measured by a rotational viscometer is 1, 1 It is preferable that it is 000 000 cSt or more.

The content of the silicone compound (B) in the present composition is a resin (A) and a compound (B) from the viewpoint that a film or a molded article which is more excellent in antifouling property to oil can be easily formed at low cost. The total amount is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, still more preferably 1 to 15% by weight, and particularly preferably 2 to 10% by weight, based on 100% by weight of the total.

<Silicone oil>
Preferably, the composition is substantially free of silicone oil. Thus, a film or a molded article excellent in long-term antifouling property can be easily obtained by substantially containing no silicone oil, and there are few components that bleed out the present composition from food containers and the like. It can be suitably used for the required applications.

The silicone oil is a compound that is oily (liquid) at normal temperature (25 ° C.), and specifically, the viscosity at 25 ° C. measured with a rotational viscometer is about 500 to 100,000 cSt, Preferably, it is a compound of 800 to 30,000 cSt.

The term "substantially free of silicone oil" means that the oil is not contained at all or, if contained, in a small amount, specifically to 100 parts by weight in total of the resin (A) and the compound (B). , Preferably less than 0.1 parts by weight.

<Additives>
In the present composition, additives other than the components (A) to (B) conventionally used for articles such as films and molded articles, specifically containers and sanitary members, according to desired applications And may be blended within a range that does not impair the effects of the present invention.
Each of the additives may be used alone or in combination of two or more.

As the additives, additives commonly used for molded products made of thermoplastic resins and thermosetting resins, for example, pigments, dyes, light stabilizers, UV absorbers, antibacterial agents, modifiers (compatibilized And / or impact modifiers), plasticizers, nucleating agents, heavy metal deactivators, stabilizing aids, antistatic agents, conductive agents, flame retardants, heat stabilizers, antioxidants, lubricants, inorganic fillers, crosslinking Polymers and fiber reinforcements.

When the additive is incorporated into the present composition, it is preferable to use an additive which has been subjected to a hydrophobization treatment in advance.
Thus, by using an additive that has been hydrophobized in advance, the effect of the additive can be achieved without impairing the antifouling effect on water and oil exerted by the combination of the components (A) and (B). Film or molded body can be formed.
When a hydrophilic additive is used as the additive, if the additive is blended as it is, the antifouling property tends to decrease. In this case, in particular, the additive which has been subjected to the hydrophobic treatment in advance is It is preferred to use.

As a method of hydrophobizing the additive, a conventionally known method can be adopted. Specifically, the additive, the hydrophobizing agent, the liquid phase method, the gas phase method, the autoclave method, etc. For example, surfactant; silicone oil; silylating agent such as alkylhalogenosilane, alkylalkoxysilane, alkyldisilazane, etc .; fluorine compound; metal soap; higher alcohol; fatty acid; rosin; It can be mentioned.
The amount of the hydrophobizing agent to be used is not particularly limited as long as it can hydrophobize the additive, and for example, it is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the additive.

Flame Retardant Depending on the application of the composition, flame retardancy may be required, and in this case, it is preferable to incorporate a flame retardant.
For example, when the present composition is used for home appliances, OA parts, Washlet (registered trademark), etc., and the resin (A) is a styrene resin, it is V-2 or more as a flame retardancy of UL 94 standard. Flame retardancy is required.

The flame retardant is not particularly limited. For example, radical trap flame retardants such as tris (tribromophenoxy) triazine, brominated epoxy oligomer, bis (pentabromophenyl) ethane, phenol addition hindered amine, butyl hydroquinone, hindered amine and the like Organically modified inorganic layered compounds such as triphenyl phosphate, phenylene bis (diphenyl phosphate), phenylene bis (di xylenyl phosphate), bisphenol A bis (diphenyl phosphate), silicone powder, zinc borate, bentonite, melamine, expanded graphite, etc. Char-forming flame retardants of the present invention; endothermic and diluting flame retardants such as aluminum hydroxide and magnesium hydroxide.

These flame retardants are suitably used for styrenic resins, and it is preferable to use them after hydrophobizing treatment in advance.
For example, in Example 3 below, when 10 parts by weight of a flame retardant or a flame retardant obtained by hydrophobizing it beforehand is blended with 100 parts by weight of ABS resin, respectively, the vertical flame retardant test of UL94 standard (thickness of test piece: The evaluation of the flame retardancy was V-2 in all cases (0.8 mm) (HB in the evaluation of the flame retardancy of Example 3), but when the flame retardant treated beforehand to be hydrophobicized is blended, Both the oleic acid contact angle and the water contact angle increased by 10 ° or more as compared with the case where the treatment flame retardant was blended.

Also, for example, in the case where the present composition is used for household appliances, OA parts, Washlet (registered trademark), etc., and the resin (A) is a propylene-based resin, V- as a flame retardancy of UL94 standard. Two or more flame retardancy is required.
In this case, the type and amount of the flame retardant may be appropriately determined in consideration of the flame retardancy required for the present composition.

As a flame retardant in this case, either an inorganic flame retardant or an organic flame retardant can be used, and by appropriately selecting these, the flame retardancy of the present composition can be made V-2 or more. it can.
Examples of the organic flame retardant include halogen flame retardants and non-halogen flame retardants, and in particular, a combination of a brominated flame retardant and an antimony compound such as antimony trioxide is typically mentioned.

The bromine-based flame retardant is not particularly limited, and examples thereof include decabromodiphenyl oxide, bis (pentabromophenyl) ethane, ethylene bis (tetrabromophthal) imide, tris (tribromophenoxy) triazine, polybromophenylindane, and ethylene. Bispentabromobenzene, decabromodiphenyl ether, tris (tribromoneopentyl) phosphate, bis [3,5-dibromo-4- (2,3-dibromopropoxy) phenyl] sulfone, bis (2,3-dibromopropyl ether) And bis (dibromopropyl) tetrabromobisphenol A and bis (dibromopropyl) tetrabromobisphenol S.
Examples of the non-halogen flame retardant include inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide, and intomescent flame retardants in which nitrogen and phosphorus are main components.

For example, in Example 4 below, when a flame retardant (brominated flame retardant and antimony trioxide) or a flame retardant obtained by hydrophobizing it in advance is blended with 100 parts by weight of PP resin (the brominated flame retardant When 15 parts by weight, 5 parts by weight of antimony trioxide) and the UL94 standard vertical flame retardant test (thickness of the test piece: 1.5 mm) were conducted, the flame retardancy was evaluated as V-0. In the evaluation of the flame retardancy of Example 4, when the flame retardant which has been hydrophobized in advance is compounded, the oleic acid contact angle and the water contact angle are both 10 as compared with the case where the untreated flame retardant is compounded. It became bigger than °.

The amount of the flame retardant to be used is preferably 1 to 150 parts by weight with respect to 100 parts by weight in total of the resin (A) and the compound (B), from the viewpoint of providing a sufficient flame retardant effect to the present composition. More preferably, it is 3 to 100 parts by weight.

-Antimicrobial agent Depending on the use of the present composition, an antimicrobial effect may be required, and in this case, it is preferable to incorporate an antimicrobial agent.
The antibacterial active substance is not particularly limited, and examples thereof include an antibacterial agent. As the antibacterial agent, a conventionally known antibacterial agent can be used, but a silver-based antibacterial agent is preferably used.

Examples of the silver-based antibacterial agent include silver-zeolite, silver-zirconium phosphate (eg, Novalon manufactured by Toagosei Co., Ltd.), silver-calcium phosphate, silver-calcium apatite, silver-silica gel, silver-calcium silicate, Examples include silver-magnesium aluminosilicate, silver-titanium oxide, silver-potassium titanate, silver-silica, alumina, silver-soluble glass, and silver-thiosulfite antibacterial agent.

The amount of the antibacterial active substance used is preferably 0.1 to 5 parts by weight to 100 parts by weight in total of the resin (A) and the compound (B) from the viewpoint that the present composition can have a sufficient antibacterial effect. Parts, more preferably 0.1 to 3 parts by weight.

Modifiers (compatibilizers and / or impact modifiers)
Since this composition contains the resin (A) and the compound (B), it is preferable to blend a modifier for improving the appearance and impact resistance.
The modifier is not particularly limited, and examples thereof include a maleic anhydride-modified propylene-based resin, a maleic anhydride-modified styrene-based resin, an olefin-based thermoplastic elastomer, and a styrene-based thermoplastic elastomer.
When a propylene-based resin is used as the resin (A) as the modifier, it is preferable to use a maleic anhydride-modified propylene-based resin, and when using a styrene-based resin as the resin (A), It is preferable to use a styrenic thermoplastic elastomer.

Examples of the styrene-based thermoplastic elastomer include SBS (styrene-butadiene-styrene block copolymer), SBBS (styrene-butadiene-butylene-styrene block copolymer), and SEBS-based (styrene-ethylene-butylene-styrene block). Copolymers) are preferred, and elastomers in which these are hydrogenated or modified with functional groups are more preferred.

The amount of the modifier used can improve the compatibility between the resin (A) and the compound (B), and / or can improve the impact resistance of the present composition, etc. From the point of view, it is preferably 1 to 30 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the resin (A) and the compound (B).

<Antifouling composition>
The present composition can be obtained by mixing the above-mentioned respective components, but the above-mentioned respective components can be obtained by a conventionally known apparatus, specifically, a single screw extruder, a twin screw extruder, a kneader, a mixer, a two roll mill. It is preferable to obtain by knead | mixing sufficiently so that it may become uniform, etc. using.

The oleic acid contact angle at 25 ± 2 ° C. of the present composition (film or molded product obtained from the present composition) is preferably 30 ° or more, more preferably 35 ° or more. Further, the water contact angle is preferably 95 ° or more, more preferably 100 ° or more.
When the oleic acid contact angle or the water contact angle is in the above range, it can be said that the antifouling property is excellent with respect to oil and other dirt components.
Specifically, the oleic acid contact angle and the water contact angle can be measured by the methods described in the following examples.

When forming a molded body from the present composition, it is preferable to mold by injection molding, and the melt flow rate measured based on JIS K 7210 of such a composition is preferably 3 to 100 g / 10 min, More preferably, it is 5 to 60 g / 10 min.

«Antifouling products»
The present composition is formed into a film or a molded article by a known method such as injection molding, extrusion molding, blow molding, calendering, vacuum molding, compression molding and gas assist molding. Products (antifouling products).
Such an antifouling product is obtained by using the present composition, and therefore, while having physical properties possessed by a propylene-based resin, a styrene-based resin, and a polyphenylene ether-based resin, it is excellent in anti-soiling properties over oil for a long time It becomes a product.
The antifouling product may be a product consisting essentially of the present composition, or a product obtained by combining a film or a molded product obtained from the present composition with another member, etc. It may be

Examples of the antifouling products include various products, and products that can be used in various fields such as household goods, food, agriculture, fishery, medical, industrial, and construction, and, particularly, toilet bowls , Toilet seat, tank, washing machine (washing nozzle), body operation switch such as washing switch, toilet paper holder, floor, toilet member such as wall; bathroom member such as floor, wall, bath, shower, faucet; washbasin, faucet , Toilet members such as soap boxes; Containers used for storing and transporting food, etc .; Kitchen members such as dishes, cutting boards, balls, triangular corners, etc .; refrigerator, washing machine, vacuum cleaner, fan, dryer, air conditioner Appliances parts such as machines, telephones, electric pots, rice cookers, dishes, dishes and dryers, microwave ovens, mixers, VTRs, TVs, watches, stereos, tape recorders, office automation equipment Fountain pen, mechanical pencil, stationery member such as ball-point pen; various medical instruments, various containers, sporting goods, daily necessaries, building materials, optics, and the like.
In the present invention, members related to the water circumference such as a bathroom, a toilet, and a washroom are collectively referred to as a sanitary member.

Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

[Examples 1 to 8 and Comparative Examples 1 to 12]
After mixing each component shown in Table 2 and Table 3 in the amount shown in Table 2 and Table 20 in a tumbler for 20 minutes, a twin screw extruder (manufactured by Toshiba Machine Co., Ltd., rotational speed: 200 rpm, screw diameter: 35 mm) The mixture was melt-kneaded at 200 to 300 ° C. using L / D: 32), extruded, and cut into a predetermined length to obtain a pellet-like resin composition.

The pellets obtained in Example 3 and Comparative Example 1 were analyzed by a reflection method using Fourier transform infrared spectroscopy (FT-IR). The analyzer used was a Fourier transform infrared spectrophotometer (model number: IRAffinity-1S) manufactured by Shimadzu Corporation. The measurement results are shown in FIGS. 1 and 2, respectively.
In the composition obtained in Example 3, the C = O stretching vibration corresponding to the ester group could be confirmed around 1730 cm ⁻¹ .

In addition, the material of Table 2 is as follows.
・ "ABS": ABS resin, manufactured by Techno Polymer Co., Ltd., ABS 130
・ "PP": polypropylene, manufactured by Sun Aroma Co., Ltd., PM 970A
・ "HIPS": Impact-resistant polystyrene, manufactured by Toyo Styrene Co., Ltd., H610
・ "M-PPE": Polyphenylene ether resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., Iupiasu AH40

“Modified silicone 1”: polyester modified silicone (in the above formula (I), R is a methyl group, at least one of R ¹ and R ² is a polyester group, and n, m and p are each independently 0 to 58, a compound wherein N = n + m + p + 2 is 15 to 75), solid (25 ° C), (commercially available)
· "Modified silicone 2": alkyl-modified silicone (in the above formula (I), R is a methyl group, and at least one of a plurality of R ¹ R ² is an alkyl group having 12 to 36 carbon atoms, n, m And p are each independently 0 to 58, and N = n + m + p + 2 is a compound of 15 to 75), solid (25 ° C), (commercially available)

・ "Unmodified silicone 1": GENIOPLAST Pellet S (Asahi Kasei Wacker Silicone Co., Ltd., pellet containing high concentration of ultra high molecular weight polydimethylsiloxane)
・ "Unmodified silicone 2": Klimbel CB-50AB (manufactured by Fuji Chemical Co., Ltd., pellet containing 50% dimethylpolysiloxane based on acrylonitrile-butadiene-styrene resin)
-"Unmodified silicone 3": DOW CORNING TORAY BY 27-004 (Toray Dow Corning Co., Ltd., pellet containing 50% dimethylpolysiloxane in HIPS (high impact polystyrene) base)
"Unmodified silicone 4": DOW CORNING TORAY MB 50-008 (made by Toray Dow Corning Co., Ltd., a pellet containing 50% dimethylpolysiloxane based on a styrene-acrylonitrile copolymer)
・ "Unmodified silicone 5": Klimbel CB-50PP (manufactured by Fuji Chemical Co., Ltd., pellet containing 50% dimethylpolysiloxane in polypropylene base)

Using the compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 12, test pieces (dimension: 90 × 50 mm, thickness: 2 mm) were produced by injection molding at a molding temperature of 200 to 300 ° C.

<Oleic acid contact angle>
2.2-2.3 μL of oleic acid (Wako Pure Chemical Industries, Ltd.) by a droplet method at a temperature of 25 ± 2 ° C. using CA-VP (manufactured by Kyowa Interface Chemicals Co., Ltd.) as a measuring apparatus The contact angle was measured when a pharmaceutical grade reagent (manufactured by Yakuhin Kogyo Co., Ltd.) was dropped onto the test piece. The results are shown in Table 2.
As the value of the contact angle is larger, it indicates that an oil-repellent test piece is obtained, and indicates that a test piece having excellent antifouling property is obtained.

<Water contact angle>
The contact angle was measured in the same manner as the oleic acid contact angle except that ultrapure water (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of oleic acid. The results are shown in Table 2.

<Stain resistance test>
The liquid mixture for wet tension test (manufactured by Wako Pure Chemical Industries, Ltd.) was obtained in Example 3, 4, 6, 8 and Comparative Example 1, 3, 7, 8, 9, 10, 11 or 12 described above. Drop one drop on each of the test pieces using the composition using a dropper (1 ml for blood collection by Polyplastics manufactured by As One Co., Ltd.), and after 5 seconds from the dropping, use the commercially available paper (Daioh Paper Co., Ltd.) Product, wipe it with a professional wipe), if it could be completely removed within 5 times, "○", if it could be completely removed by 10-30 times, "△", 30 or more wipes were required to completely remove The case where it did was made "x". In the case of the test pieces of Examples 3, 6, 8 and Comparative Examples 1, 3, 9, 10, 11, 12, the mixture for wet tension test (Wako Pure Chemical Industries, Ltd., No. 36.0) In the case of the test pieces of Example 4 and Comparative Examples 7 and 8, a mixed solution for wet tension test (No. 22.6 manufactured by Wako Pure Chemical Industries, Ltd.) was used. The results are shown in Table 3.
The operation of passing the paper with a load of 100 to 200 g to the droplet portion was regarded as one wiping, and it was visually confirmed whether the droplets could be completely removed.

Claims (14)

1. Containing at least one resin (A) selected from propylene resins, styrene resins and polyphenylene ether resins, and a polyester-modified or alkyl-modified silicone compound (B) which is solid at 25 ° C. Staining composition.
2. The antifouling composition according to claim 1, wherein the resin (A) is a styrene resin, and the silicone compound (B) is a polyester-modified silicone compound which is solid at 25 ° C.
3. The antifouling composition according to claim 1 or 2, wherein the silicone compound (B) is a compound represented by the following formula (I).
   

   

   [In the formula (I),
   R is, independently of one another, a hydrocarbon group having 1 to 12 carbon atoms,
   R ¹ and R ² are, independently of each other, a polyester group, a hydrocarbon group having 1 to 36 carbon atoms, or a group in which a part of the hydrocarbon group is substituted with an oxygen atom,
   n, m and p are each independently 0 to 58,
   N = n + m + p + 2 is 10 to 75,
   At least one of all R ¹ and R ² is a polyester group or an alkyl group having 12 to 36 carbon atoms. ]
4. The antifouling composition according to claim 3, wherein the polyester group is a group represented by the following formula (II).
   -R ^q- (R ^r ) _z H (II)
   [In the formula (II), R ^q is a group represented by — (CH ₂ ) _x —O— (x is 2 to 10,
   R ^r is a group represented by —C (= O) — (CH ₂ ) _y —O— (y is 2 to 10),
   z is 3-30. ]
5. The antifouling composition according to claim 3, wherein at least one of R ¹ and R ² is a polyester group.
6. The content of the said silicone compound (B) is 0.1-30 weight% with respect to a total of 100 weight% of the said resin (A) and a compound (B), It is any one of Claims 1-5. Antifouling composition.
7. The antifouling composition according to any one of claims 1 to 6, which is substantially free of silicone oil.
8. Pigments, dyes, light stabilizers, UV absorbers, antibacterial agents, modifiers, plasticizers, nucleating agents, heavy metal deactivators, stabilizing aids, antistatic agents, conductive agents, flame retardants, thermal stabilizers The antifouling composition according to any one of claims 1 to 7, comprising one or more additives selected from an antioxidant, a lubricant, an inorganic filler, a crosslinkable polymer and a fiber reinforcing agent.
9. The antifouling composition according to claim 8, wherein the additive is a hydrophobized additive.
10. A container obtained using the antifouling composition according to any one of claims 1 to 9.
11. A sanitary member obtained using the antifouling composition according to any one of claims 1 to 9.
12. A kitchen member obtained by using the antifouling composition according to any one of claims 1 to 9.
13. A household electric appliance member obtained by using the antifouling composition according to any one of claims 1 to 9.
14. A stationery member obtained using the antifouling composition according to any one of claims 1 to 9.

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