JP2021050300A - Additive for resin - Google Patents

Abstract

To provide a technology which is capable of uniformly imparting a resin with excellent water- and oil-repellent properties.SOLUTION: An additive for resin contains a copolymer that is obtained by polymerizing constituent monomers which contain (a1) a (meth)acrylate compound that has a fluoroalkyl group having from 1 to 6 carbon atoms, (a2) a non-fluorine (meth)acrylate compound that has a linear or branched chain aliphatic hydrocarbon, and (a3) a non-fluorine (meth)acrylate compound that has an aromatic group.SELECTED DRAWING: None

Description

The present invention relates to additives for resins.

Conventionally, as a method of imparting water and oil repellency to a resin, a method of adding a fluorine-based polymer to the resin has been known (for example, Patent Documents 1 and 2).

Reference 1 describes a method of adding a copolymer of stearyl methacrylate and 2-perfluorohexyl ethyl methacrylate to an olefin resin. Further, Reference 2 describes a method of adding a copolymer of a fluorine-containing acrylate ester and a stearyl (meth) acrylate to a thermoplastic resin.

Japanese Unexamined Patent Publication No. 03-7745 Japanese Unexamined Patent Publication No. 2006-37085

It is true that the copolymers described in Patent Documents 1 and 2 are uniformly compatible with the resin in appearance, and it seems that water and oil repellency can be imparted. However, as a result of actual tests conducted by the present inventors, it has been found that the water and oil repellency varies depending on the location, and there is a problem that water and oil permeate from a location having low water and oil repellency. Although the mechanism is not clear, it is considered that phase separation occurs by forming an island-like structure by agglutination of the copolymer in the resin, and thus the water repellency and oil repellency vary from place to place. Therefore, it is desired to develop a technique capable of uniformly imparting excellent water and oil repellency to the resin.

The present invention has been made to solve the above problems, and can be realized as the following forms.

(1) According to one embodiment of the present invention, an additive for a resin is provided. This resin additive is
A (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and
A non-fluorine (meth) acrylate compound (a2) having a linear or branched aliphatic hydrocarbon,
A non-fluorine (meth) acrylate compound (a3) having an aromatic group and
Contains a copolymer obtained by polymerizing a constituent monomer containing.

According to this form of additive for resin, excellent water and oil repellency can be uniformly imparted to the resin.

(2) In the resin additive of the above embodiment, the number of carbon atoms in the aliphatic hydrocarbon moiety of the non-fluorine (meth) acrylate compound (a2) having a linear or branched aliphatic hydrocarbon is 10 or more. May be good.

According to this form of additive for resin, it is possible to give a uniform appearance by improving the compatibility with the resin and to impart excellent water and oil repellency to the resin more uniformly.

(3) In the resin additive of the above-mentioned form, benzyl methacrylate may be contained as the non-fluorine (meth) acrylate compound (a3) having the aromatic group.

According to this form of additive for resin, excellent water and oil repellency can be more uniformly imparted to the resin.

(4) In the above-mentioned additive for resin, the amount of the non-fluorine (meth) acrylate compound (a2) having a linear or branched aliphatic hydrocarbon is the fluoroalkyl group having 1 to 6 carbon atoms. It may be 20 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the (meth) acrylate compound (a1) having.

According to this form of additive for resin, it is possible to give a uniform appearance by improving the compatibility with the resin and to impart excellent water and oil repellency to the resin more uniformly.

(5) In the resin additive of the above embodiment, the amount of the non-fluorine (meth) acrylate compound (a3) having an aromatic group is the (meth) acrylate compound having a fluoroalkyl group having 1 to 6 carbon atoms. (A1) It may be 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass.

According to this form of additive for resin, more excellent water and oil repellency can be uniformly imparted to the resin.

(6) In the above-mentioned resin additive, the amount of the non-fluoro (meth) acrylate compound (a3) having the aromatic group is the non-fluorine (meth) having the linear or branched aliphatic hydrocarbon. ) The acrylate compound (a2) may be 15 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass.

According to this form of additive for resin, excellent water and oil repellency can be more uniformly imparted to the resin.

(7) The glass transition temperature of the homopolymer obtained by polymerizing the non-fluorine (meth) acrylate compound (a2) having a linear or branched aliphatic hydrocarbon in the above-mentioned resin additive has a glass transition temperature. It may be 10 ° C. or higher.

According to this form of additive for resin, excellent water and oil repellency can be more uniformly imparted to the resin.

The present invention can be realized in various forms, for example, in the form of an additive for a coating resin or the like.

A. Additives for Resins Additives for resins according to an embodiment of the present invention include (i) a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and (ii) a linear or branched chain. Obtained by polymerizing a constituent monomer containing a non-fluorine (meth) acrylate compound (a2) having an aliphatic hydrocarbon of (iii) and a non-fluorine (meth) acrylate compound (a3) having an aromatic group (iii). Contains a copolymer. In addition, in this specification, "(meth) acrylate" means acrylate or methacrylate. Further, in the present specification, the "constituting monomer" means a monomer constituting a copolymer. Further, the "(meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms" is also hereinafter referred to as "(meth) acrylate compound (a1)". Similarly, a "non-fluorine (meth) acrylate compound (a2) having a linear or branched aliphatic hydrocarbon" is also referred to as a "non-fluorine (meth) acrylate compound (a2)" and has an "aromatic group". The "non-fluorine (meth) acrylate compound (a3)" is also referred to as a "non-fluorine (meth) acrylate compound (a3)".

According to the resin additive of the present embodiment, excellent water and oil repellency can be uniformly imparted to the resin. Hereinafter, the constituent monomers of the resin additive of the present embodiment will be described.

<(Meta) acrylate compound (a1)>
The (meth) acrylate compound (a1) of the present embodiment has a fluoroalkyl group having 1 to 6 carbon atoms. Examples of the (meth) acrylate compound (a1) include fluoroalkyl (meth) acrylate, fluoroalkylalkyl (meth) acrylate, and fluoroalkylpolyoxyfluoroalkylene (meth) acrylate. Of these, fluoroalkyl (meth) acrylate and fluoroalkylalkyl (meth) acrylate are preferable, and fluoroalkylalkyl (meth) acrylate is more preferable, because they are excellent in water and oil repellency. Since the fluoroalkyl group is excellent in water and oil repellency, it is preferably a fluoroalkyl group having 2 to 6 carbon atoms, more preferably a fluoroalkyl group having 4 to 6 carbon atoms, and a fluoroalkyl group having 6 carbon atoms. It is more preferably an alkyl group. Here, in the present specification, "fluoro" includes perfluoro. The fluoroalkyl group is preferably a perfluoroalkyl group.

Examples of the fluoroalkyl (meth) acrylate include fluoromethyl (meth) acrylate, fluoroethyl (meth) acrylate, fluoropropyl (meth) acrylate, fluorobutyl (meth) acrylate, fluoropentyl (meth) acrylate, and fluorohexyl (meth). ) Acrylate and the like can be mentioned.

Here, the fluoroalkyl (meth) acrylate can also be represented by the following general formula (1).
Rf-OX ... (1)
However, Rf is a fluoroalkyl group and X is an acryloyl group or a methacryloyl group.

Examples of the fluoroalkylalkyl (meth) acrylate include fluoromethylmethyl (meth) acrylate, fluoromethylethyl (meth) acrylate, fluoroethylmethyl (meth) acrylate, fluoroethylethyl (meth) acrylate, and fluoropropylmethyl (meth) acrylate. Acrylate, fluoropropyl ethyl (meth) acrylate, fluorobutylmethyl (meth) acrylate, fluorobutylethyl (meth) acrylate, fluoropentylmethyl (meth) acrylate, fluoropentylethyl (meth) acrylate, fluorohexylmethyl (meth) acrylate, Fluorohexyl ethyl (meth) acrylate and the like can be mentioned. The fluoroalkylalkyl (meth) acrylate can also be represented by the following general formula (2).
Rf-Y-O-X ... (2)
However, Rf is a fluoroalkyl group, Y is an alkylene group, and X is an acryloyl group or a methacryloyl group.

Examples of the fluoroalkyl polyoxyfluoroalkylene (meth) acrylate include fluoromethyl polyoxyfluoroethylene (meth) acrylate, fluoroethyl polyoxyfluoroethylene (meth) acrylate, fluoropropyl polyoxyfluoroethylene (meth) acrylate, and fluorobutyl. Examples thereof include polyoxyfluoroethylene (meth) acrylate, fluoropentyl polyoxyfluoroethylene (meth) acrylate, fluorohexyl polyoxyfluoroethylene (meth) acrylate, and fluorohexyl polyoxyfluoropropylene (meth) acrylate. The fluoroalkyl polyoxyfluoroalkylene (meth) acrylate can also be represented by the following general formula (3).
Rf-Z-O-X ... (3)
However, Rf is a fluoroalkyl group, Z is a polyoxyfluoroalkylene group, and X is an acryloyl group or a methacryloyl group.

As the (meth) acrylate compound (a1), fluoroalkyl (meth) acrylate and fluoroalkylalkyl (meth) acrylate are preferable, and fluoroalkylalkyl (meth) acrylate is more preferable, because they are excellent in water and oil repellency. Further, as the fluoroalkyl group, a perfluoroalkyl group is preferable because it has excellent water and oil repellency. Specifically, as the (meth) acrylate compound (a1), perfluorohexylmethyl (meth) acrylate and perfluorohexylethyl (meth) acrylate are preferable because they are excellent in water and oil repellency.

The α-substituted group at the acrylate moiety in the (meth) acrylate compound (a1) is not particularly limited, and examples thereof include a hydrogen atom, a methyl group, and other monovalent organic groups. Of these, hydrogen atoms and methyl groups are preferable as the α-substituted group because they are more excellent in water repellency and oil repellency.

<Non-fluorine (meth) acrylate compound (a2)>
The non-fluorine (meth) acrylate compound (a2) in the present embodiment is a fluorine-free (meth) acrylate compound and is a (meth) acrylate compound having a linear or branched aliphatic hydrocarbon.

The non-fluorine (meth) acrylate compound having a linear aliphatic hydrocarbon is not particularly limited, and is, for example, n-butyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, and palmityl (meth). Examples thereof include meta) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.

The non-fluorinated (meth) acrylate compound having a branched aliphatic hydrocarbon is not particularly limited, and for example, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and isodecyl (meth). Examples thereof include acrylate, isostearyl (meth) acrylate, and isoamyl (meth) acrylate.

The carbon number of the aliphatic hydrocarbon moiety in the non-fluorine (meth) acrylate compound (a2) is not particularly limited, but the carbon number is 8 or more from the viewpoint of uniformly imparting excellent water and oil repellency to the resin. It is preferably, more preferably 10 or more, and even more preferably 12 or more. Similarly, from the viewpoint of uniformly imparting excellent water and oil repellency to the resin, the carbon number of the aliphatic hydrocarbon moiety in the non-fluorine (meth) acrylate compound (a2) is preferably 22 or less. It is more preferably 20 or less, and further preferably 19 or less. By keeping the carbon number of the aliphatic hydrocarbon moiety in the non-fluorine (meth) acrylate compound (a2) within the above preferable range, the compatibility with the resin is also excellent, and the appearance when the added resin is used as a molded product Is also excellent.

The glass transition temperature of the homopolymer obtained by polymerizing the non-fluorine (meth) acrylate compound (a2) is not particularly limited, but is preferably 0 ° C. or higher from the viewpoint of uniformly imparting excellent water and oil repellency to the resin. 10 ° C. or higher is more preferable, and 30 ° C. or higher is even more preferable.

<Non-fluorine (meth) acrylate compound (a3)>
The non-fluorine (meth) acrylate compound (a3) in the present embodiment is a fluorine-free (meth) acrylate compound and is a (meth) acrylate compound having an aromatic group.

The non-fluorine (meth) acrylate compound (a3) of the present embodiment is not particularly limited, but for example, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenyl (meth) acrylate and the like. Can be mentioned. From the viewpoint of uniformly imparting excellent water and oil repellency to the resin, the non-fluorine (meth) acrylate compound (a3) of the present embodiment includes phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and benzyl. (Meta) acrylates are more preferred, benzyl (meth) acrylates are even more preferred, and benzyl methacrylates are particularly preferred.

The constituent monomers constituting the copolymer of the present embodiment may contain monomers other than the above-mentioned components (a1), (a2) and (a3) as long as they do not contradict the object of the invention. Similarly, the resin additive of the present embodiment may contain a copolymer other than the above-mentioned copolymer as long as it does not contradict the object of the invention. However, when a monomer containing a crosslinkable group is used as a constituent monomer constituting the copolymer of the present embodiment, segregation on the resin surface may be hindered by the copolymer having a network structure. Therefore, it may not be preferable.

In the present embodiment, the total blending amount of the (meth) acrylate compound (a1), the non-fluorine (meth) acrylate compound (a2), and the non-fluorine (meth) acrylate compound (a3) with respect to the total blending amount of the constituent monomers is Although not particularly limited, it is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more, from the viewpoint of uniformly imparting excellent water and oil repellency to the resin. It is more preferable to have. The total amount of the (meth) acrylate compound (a1), the non-fluorine (meth) acrylate compound (a2), and the non-fluorine (meth) acrylate compound (a3) with respect to the total amount of the constituent monomers is 100 mass. % Or less.

The amount of the non-fluorine (meth) acrylate compound (a2) to be blended is not particularly limited, but from the viewpoint of uniformly imparting excellent water and oil repellency to the resin, the amount of the (meth) acrylate compound (a1) is 100 parts by mass. On the other hand, 10 parts by mass or more is preferable, 15 parts by mass or more is more preferable, 20 parts by mass or more is further preferable, and 30 parts by mass or more is particularly preferable. Similarly, the blending amount of the non-fluorine (meth) acrylate compound (a2) is based on 100 parts by mass of the (meth) acrylate compound (a1) from the viewpoint of uniformly imparting excellent water and oil repellency to the resin. , 100 parts by mass or less, more preferably 90 parts by mass or less, further preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less.

The amount of the non-fluorine (meth) acrylate compound (a3) to be blended is not particularly limited, but from the viewpoint of uniformly imparting excellent water and oil repellency to the resin, the amount of the (meth) acrylate compound (a1) is 100 parts by mass. On the other hand, 5 parts by mass or more is preferable, 10 parts by mass or more is more preferable, 15 parts by mass or more is further preferable, and 20 parts by mass or more is particularly preferable. Similarly, the blending amount of the non-fluorine (meth) acrylate compound (a3) is based on 100 parts by mass of the (meth) acrylate compound (a1) from the viewpoint of uniformly imparting excellent water and oil repellency to the resin. , 80 parts by mass or less, more preferably 70 parts by mass or less, further preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less.

Further, the blending amount of the non-fluorine (meth) acrylate compound (a3) is based on 100 parts by mass of the non-fluorine (meth) acrylate compound (a2) from the viewpoint of uniformly imparting excellent water and oil repellency to the resin. 5 parts by mass or more is preferable, 10 parts by mass or more is more preferable, 15 parts by mass or more is further preferable, and 30 parts by mass or more is particularly preferable. Similarly, the blending amount of the non-fluorine (meth) acrylate compound (a3) is 100 parts by mass of the non-fluorine (meth) acrylate compound (a2) from the viewpoint of uniformly imparting excellent water and oil repellency to the resin. On the other hand, 180 parts by mass or less is preferable, 160 parts by mass or less is more preferable, 150 parts by mass or less is further preferable, and 120 parts by mass or less is particularly preferable.

The solvent used for the resin additive of the present embodiment is not particularly limited, and may be, for example, an organic solvent. Examples of the organic solvent include aromatic solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane and isophorone, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, propyl acetate, propylene glycol diacetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol Glycol ether ester solvents such as monoethyl ether acetate and 3-methoxy-3-methylbutyl acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol dibutyl ether, dimethyltriglycol, methylethyldiglycol , Glycol ether solvents such as dimethyl propylene diglycol, dimethyl sulfoxide, dimethyl formamide, N-methyl-2-pyrrolidone and the like, among which acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, propyl acetate, etc. It is preferably ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methyl ethyl diglycol, propylene glycol monomethyl ether acetate, 3-methoxy-3-methylbutyl acetate, or dimethyl propylene diglycol.

The resin to which the resin additive of the present embodiment is added is not particularly limited, and examples thereof include a thermoplastic resin and a curable resin.

The thermoplastic resin is not particularly limited, but for example, polyacrylate resin, polystyrene resin, polyester resin, polyolefin resin, polyether resin, ABS resin, polyacetal resin, polyvinyl chloride resin, polypropylene resin, polyethylene resin, polyurethane resin and the like. Can be mentioned. In particular, among the above-mentioned resins, polyacrylate resin, polystyrene resin, polyurethane resin, and polyester resin are preferable from the viewpoint of exhibiting uniform and high water and oil repellency by adding the resin additive of the present embodiment. Polyacrylate resin and polystyrene resin are more preferable.

The curable resin is not particularly limited, and examples thereof include a photocurable resin and a thermosetting resin. The photocurable resin is not particularly limited, and for example, urethane acrylate, epoxy acrylate, acrylic acrylate, polyester acrylate, polyfunctional acrylate and the like are used as benzophenone-based, acetophenone-based, benzoin ether-based, thioxanthone-based photopolymerization initiators. Examples include those cured with. Examples of the thermosetting resin include epoxy resin, phenol resin, urea resin, melamine resin, polyimide, polyurethane and the like.

The method of adding the resin additive of the present embodiment to the resin is not particularly limited, and examples thereof include a method of mixing the resin and the resin additive of the present embodiment. Specific examples thereof include a method in which the resin is melted or dissolved in a solvent, the resin additive of the present embodiment is added, and then the resin is mixed. The resin composition obtained by mixing the resin and the resin additive of the present embodiment may be used as a coating agent, or may be cured and used as a resin molded product. The method of molding as a resin molded body is not particularly limited, and for example, in the case of a thermoplastic resin, ordinary resin molding methods such as injection molding, blow molding, extrusion molding, hollow molding, calender molding, and press molding can be mentioned. Further, in the case of a curable resin, as a molding method, for example, a method of preparing a pre-curing resin composition to which the resin additive of the present embodiment is added, molding the resin composition, and then curing the resin composition by heat or light is used. Can be mentioned. When the resin composition is used as a coating agent, a coating layer can be formed by applying it on a base material such as metal, glass, or resin.

The amount of the resin additive of the present embodiment added to the resin is not particularly limited, but is preferably 0.1% by mass or more and 10% by mass or less, and 1.0% by mass or more and 7. 5% by mass or less is more preferable, and 1.5% by mass or more and 5.0% by mass or less is further preferable.

Next, a method for producing the resin additive of the present embodiment will be described. The method for producing the resin additive is not particularly limited. Examples of the method for producing the resin additive include a (meth) acrylate compound (a1), a non-fluorine (meth) acrylate compound (a2), a non-fluorine (meth) acrylate compound (a3), and a solvent. Examples thereof include a method of obtaining a copolymer by heating after mixing.

The polymerization method is not particularly limited, but solution polymerization is preferable. The polymerization temperature is not particularly limited, but is generally preferably in the range of 40 ° C. or higher and 120 ° C. or lower. The polymerization time is not particularly limited, but is generally preferably about 4 to 15 hours.

A polymerization initiator may be used when carrying out the polymerization. The polymerization initiator is not particularly limited, but for example, benzoyl peroxide, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, 1,1 , 3,3-Tetramethylbutylperoxy-2-ethylhexanoate and other peroxides, azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile and other azo compounds and the like. .. The amount of the polymerization initiator used is not particularly limited, but is generally preferably 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the constituent monomer.

The resin additive of the present embodiment is, for example, other oil repellent, other water repellent, insect repellent, flame retardant, wrinkle repellent, antistatic agent, soft finishing agent, within a range not contrary to the object of the invention. It may further contain preservatives, fragrances, antioxidants, emulsifiers, dispersants and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In addition, "part" and "%" in this specification represent "part by mass" and "% by mass", respectively, unless otherwise specified.

(Ingredients used)
-A (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms.
(A1-1) Perfluorohexyl ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
(A1-2) Perfluorobutylethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

-Non-fluorine (meth) acrylate compound (a2) having a linear or branched aliphatic hydrocarbon
(A2-1) Stearyl Methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light ester S, glass transition point: 38 ° C., carbon number of aliphatic hydrocarbon moiety: 18)
(A2-2) Isodecyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light ester ID, glass transition point: −41 ° C., carbon number of aliphatic hydrocarbon moiety: 10)
(a2-3) 2-Ethylhexyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light ester ID, glass transition point: -10 ° C, carbon number of aliphatic hydrocarbon moiety: 8)
(A2-4) Lauryl Methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light ester L, glass transition point: -65 ° C, carbon number of aliphatic hydrocarbon moiety: 12)

-Non-fluorine (meth) acrylate compound (a3) having an aromatic group
(A3-1) Benzyl Methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Ester B
Z)

(Copolymer A-1)
The compounds of (a1), (a2), and (a3) and ethyl acetate as a solvent are placed in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux tube in the mass ratios shown in Table 1 described later. 300 parts were added and nitrogen substitution was performed. Subsequently, t-butyl peroxypivalate (manufactured by Nichiyu Co., Ltd., trade name: Perbutyl (registered trademark) PV) is added to 100 parts by mass of the total amount of the compounds (a1), (a2) and (a3). A copolymer (solid content of the copolymer: 25% by mass) was obtained by adding the amount to 3 parts by mass and reacting at 65 ° C. for 8 hours.

(Copolymers other than copolymer A-1 and comparative copolymers)
For copolymers other than copolymer A-1, and comparative copolymers, the copolymer solutions are prepared in the same manner as in copolymer A-1 using the materials and mass ratios shown in Tables 1 and 2 described later. Got

(Example 1)
After mixing 0.1 part by mass of the obtained copolymer A-1, 1 part by mass of polymethyl methacrylate (PMMA, manufactured by Nacalai Tesque, Inc., average degree of polymerization of about 8000) and 19 parts by mass of ethyl acetate, A coating agent was prepared by heating and dissolving at 70 ° C. Then, the coating agent was applied onto a glass plate by a bar coater method so that the film thickness was 10 μm, and then dried in an oven at 80 ° C. for 10 minutes to prepare a test piece.

(Example 2)
A test piece was prepared by the same method as in Example 1 except that polystyrene (PS, PSJ-polystyrene G9305, manufactured by PS Japan Corporation) was used instead of PMMA as compared with Example 1.

(Example 3)
3 parts by mass of the obtained copolymer A-1, dipentaerythritol hexaacrylate (DPHA, KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 27 parts by mass, 1-hydroxycyclohexylphenyl ketone (Irgacure 184, BASF Japan) Co., Ltd.) and 70 parts by mass of ethyl acetate were mixed to prepare a coating agent. Then, the coating agent was applied onto a glass plate by a bar coater method so that the film thickness was 10 μm, and then dried in an oven at 80 ° C. for 1 minute. After that, using a UV irradiation device (CSN2-4, manufactured by GS Yuasa Co., Ltd.) using a high-pressure mercury lamp, ultraviolet irradiation is performed under the conditions of a conveyor speed of 5 m / min, a distance from the lamp of 8 cm, and an integrated illuminance of 800 mJ / cm ^2. By doing so, a test piece was prepared.

(Examples 4 to 13)
A test piece was prepared by the same method as in Example 1 except that the copolymers A-2 to A-11 were used instead of the copolymer A-1 as compared with Example 1.

(Example 14)
A test piece was prepared by the same method as in Example 1 except that 0.04 part by mass of the copolymer A-1 was used instead of 0.1 part by mass as compared with Example 1.

(Example 15)
A test piece was prepared by the same method as in Example 1 except that 0.2 parts by mass of the copolymer A-1 was used instead of 0.1 parts by mass as compared with Example 1.

(Example 16)
A test piece was prepared by the same method as in Example 1 except that 0.4 parts by mass of the copolymer A-1 was used instead of 0.1 parts by mass as compared with Example 1.

(Comparative Example 1)
A test piece was prepared by the same method as in Example 1 except that the comparative copolymer A-12 was used instead of the copolymer A-1 as compared with Example 1.

(Comparative Example 2)
A test piece was prepared by the same method as in Example 2 except that the comparative copolymer A-12 was used instead of the copolymer A-1 as compared with Example 2.

(Comparative Example 3)
A test piece was prepared by the same method as in Example 3 except that the comparative copolymer A-12 was used instead of the copolymer A-1 as compared with Example 3.

(Comparative Examples 4 to 8)
A test piece was prepared by the same method as in Example 1 except that the comparative copolymers A-13 to A-17 were used instead of the copolymer A-1 as compared with Example 1.

(Evaluation of appearance)
The appearance was visually evaluated in the following three stages.
A: Uniform appearance B: Slightly turbid or uneven C: Turbidity or unevenness

(Evaluation method of water repellency and oil repellency)
The water repellency and oil repellency were evaluated using a contact angle measuring device (contact angle meter Drop Master 500 manufactured by Kyowa Interface Science Co., Ltd.). Specifically, the water repellency was evaluated by measuring the contact angle of water on the coated surface, and the oil repellency was evaluated by measuring the contact angle of hexadecane on the coated surface. Water repellency was evaluated by water contact angle, and oil repellency was evaluated by hexadecane contact angle. The droplet volume of water was 2 μL, and the droplet volume of hexadecane was 4 μL. Each evaluation was performed by measuring the contact angle 5 seconds after dropping. In the evaluation, the average value measured 5 times at different locations was used.

The water repellency was evaluated in the following five stages. The larger the contact angle, the better the water repellency, which is preferable.
A: Contact angle is 110 ° or more B: Contact angle is 100 ° or more and less than 110 ° C: Contact angle is less than 100 °

The oil repellency was evaluated on the following five stages. The larger the contact angle, the better the oil repellency, which is preferable.
A: Contact angle is 50 ° or more B: Contact angle is 40 ° or more and less than 50 ° C: Contact angle is 30 ° or more and less than 40 ° D: Contact angle is less than 30 °

(Evaluation method of variation in water repellency and variation in oil repellency)
For the evaluation of the variation in water repellency and the variation in oil repellency, the contact angle was measured 10 times at different measurement locations, and the coefficient of variation of the contact angle was used. Specifically, the variation in water repellency and the variation in oil repellency were evaluated in the following five stages, respectively. The smaller the value, the smaller the variation, which is preferable.
A: Coefficient of variation is less than 0.01 B: Coefficient of variation is 0.01 or more and less than 0.03 C: Coefficient of variation is 0.03 or more and less than 0.05 D: Coefficient of variation is 0.05 or more

The following was found from Tables 3 to 5 showing the evaluation results of Examples and Comparative Examples. That is, a constituent monomer containing a non-fluorine (meth) acrylate compound (a2) having a linear or branched aliphatic hydrocarbon and a non-fluorine (meth) acrylate compound (a3) having an aromatic group is polymerized. It was found that Examples 1 to 16 containing the obtained copolymers had less variation in water repellency and oil repellency as compared with Comparative Examples 1 to 8 not containing them. That is, it was found that the resin additive of the present embodiment can uniformly impart excellent water and oil repellency to the resin.

Further, even when the resin additive of the present embodiment is added to different resins from Examples 1, 2 and 3, the resin additive of the present embodiment has excellent water repellency and water repellency to the resin. It was found that the oiliness can be uniformly applied.

Further, by comparing Examples 1, 4-6, Examples 1, 4 and 6 in which the number of carbon atoms of the aliphatic hydrocarbon moiety in the non-fluorine (meth) acrylate compound (a2) is 10 or more are the carbons. It was found to be superior to Example 5 in which the number was less than 10 in terms of variation in oil repellency.

Further, by comparing Examples 1 and 4-6, Example 1 in which the glass transition temperature of the homopolymer obtained by polymerizing the non-fluorine (meth) acrylate compound (a2) is 10 ° C. or higher is determined. It was found that this temperature tends to be comprehensively superior to that of Example 4-6 in which the temperature is less than 10 ° C. in terms of variation in water repellency and oil repellency.

Further, by comparing Examples 1 and 4-16, the blending amount of the non-fluorine (meth) acrylate compound (a3) is 10 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the (meth) acrylate compound (a1). Examples 1, 4-8 and 10-16, which are less than or equal to parts, are comprehensively compared with Example 9 in which the compounding amount is larger than 50 parts by mass in terms of variations in water and oil repellency and water and oil repellency. It turns out that it tends to be superior.

<Impossible / impractical circumstances>
The resin additive of the present embodiment includes a (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a non-fluorine (meth) acrylate compound having a linear or branched aliphatic hydrocarbon. It contains a copolymer obtained by polymerizing a constituent monomer containing (a2) and a non-fluorine (meth) acrylate compound (a3) having an aromatic group. Since the structure of this copolymer is complicated, it is difficult to express it by a general formula. Furthermore, if the structure is not specified, the properties of the substance that are determined accordingly cannot be easily determined. That is, it is impossible to directly specify the copolymer contained in the resin additive of the present embodiment by its structure or characteristics.

Since the resin additive of the present embodiment can uniformly impart excellent water and oil repellency to the resin, resin molding is particularly required to uniformly impart excellent water and oil repellency. It can be suitably used for the body and coating agents. When the resin additive of the present embodiment is used for the resin molded product or the coating agent, the components of the resin additive of the present embodiment are exposed on the surface of the resin molded product or the coating layer, resulting in excellent water repellency and water repellency. The oiliness can be uniformly imparted. Examples of applications include automobile parts, building materials, electronic devices, home appliances, and the like.

The present invention is not limited to the above-described embodiment, and can be realized with various configurations within a range not deviating from the gist thereof. For example, the embodiment corresponding to the technical feature in each embodiment described in the column of the outline of the invention, the technical feature in the embodiment may be used to solve a part or all of the above-mentioned problems, or the above-mentioned above. It is possible to replace or combine them as appropriate to achieve some or all of the effects. Further, if the technical feature is not described as essential in the present specification, it can be deleted as appropriate.

Claims (8)

A (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and
A non-fluorine (meth) acrylate compound (a2) having a linear or branched aliphatic hydrocarbon,
A non-fluorine (meth) acrylate compound (a3) having an aromatic group and
Additive for resin containing a copolymer obtained by polymerizing a constituent monomer containing. The resin additive according to claim 1, wherein the non-fluorine (meth) acrylate compound (a2) having a linear or branched aliphatic hydrocarbon has 10 or more carbon atoms at the aliphatic hydrocarbon moiety. The resin additive according to claim 1 or 2, which contains benzyl methacrylate as the non-fluorine (meth) acrylate compound (a3) having an aromatic group. The blending amount of the non-fluorine (meth) acrylate compound (a2) having a linear or branched aliphatic hydrocarbon is 100 mass by mass of the (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms. The resin additive according to any one of claims 1 to 3, wherein the amount is 20 parts by mass or more and 80 parts by mass or less with respect to the portion. The blending amount of the non-fluorine (meth) acrylate compound (a3) having an aromatic group is 10 parts by mass with respect to 100 parts by mass of the (meth) acrylate compound (a1) having a fluoroalkyl group having 1 to 6 carbon atoms. The resin additive according to any one of claims 1 to 4, which is 50 parts by mass or less. The blending amount of the non-fluorine (meth) acrylate compound (a3) having an aromatic group is 100 parts by mass of the non-fluorine (meth) acrylate compound (a2) having a linear or branched aliphatic hydrocarbon. The resin additive according to any one of claims 1 to 5, which is 15 parts by mass or more and 150 parts by mass or less. Claims 1 to claim 1 to claim 1, wherein the glass transition temperature of the homopolymer obtained by polymerizing the non-fluorine (meth) acrylate compound (a2) having a linear or branched aliphatic hydrocarbon is 10 ° C. or higher. The resin additive according to any one of up to 6. The resin additive according to any one of claims 1 to 7, which is used as an additive for a coating resin.