JPH0127094B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an interface-modifying composition suitable for coating on the surface of a synthetic resin molded article, and a synthetic resin film coated with the same. Conventionally, methods for changing the surface properties of synthetic resin molded products such as synthetic resin films, such as anti-static treatment, prevention of water droplet adhesion, anti-fogging (anti-fog), anti-fouling, anti-blocking treatment methods, have mainly been carried out using various methods. A method has been adopted in which a surfactant having a certain property is kneaded into a synthetic resin or coated on the surface of a synthetic resin molded product. In the former case, the surfactant migrates and diffuses (bleeds) onto the surface of the molded product over time, so by selecting a surfactant with suitable bleedability, the surface of the molded product can be left in a modified state for a long time. However, it is not as effective as the coating method immediately after molding.
Moreover, the effect is small compared to molded products coated even after a certain period of time. Furthermore, when changing the properties of the surface of a molded product by kneading a surfactant, it is necessary to take into account the thermal history during the manufacture of the molded product.In other words, it is necessary to select a surfactant that will not decompose or thermally deteriorate during heating. There is also the drawback that the types are naturally limited. However, although the latter method has an extremely large modification effect compared to the kneading method, and the surfactant can be freely selected and is simple, the coating method is now almost always used except in special cases. It has not been. The reasons why the coating method is not adopted include, for example, when a surfactant is applied directly to the surface of a molded product, the concentration of the surfactant is too high, so it is not applied evenly, and even if it is applied, it easily falls off when washed or touched. When a surfactant is diluted with water, the surface tension of the water is greater than the critical surface tension of the surface of the molded product, so the water itself forms droplets on the surface of the molded product, and when the surfactant is diluted with organic solvents such as alcohol and acetone, the solvent evaporates quickly and is not applied evenly. For example, even if it can be applied, problems such as environmental pollution due to the vaporization of the solvent remain, and furthermore, since it does not permeate and diffuse into the interior of the molded product, it easily falls off when washed with water, etc., and its properties cannot be maintained for a long time. can be mentioned. Therefore, the coating method is only used when the kneading method is insufficiently effective or when sustainability is not required. The inventor of the present invention conducted extensive research on a method that can maintain the modification effect for a long period of time, focusing on antifogging treatment, regarding the conventional coating method that exerts a great effect on modification by applying it to the surface of the molded product. By using a plasticizer used for synthetic resins, which is not normally used as a solvent for surfactants, it is possible to uniformly apply the surfactant to the surface of the synthetic resin molded product. The plasticizer permeates and absorbs into the synthetic resin molded product, and at the same time, the surfactant contained in the plasticizer also permeates and diffuses into the molded product, exerting an extremely large surface modification effect and maintaining its surface properties for a long period of time. We found that it is possible to maintain a denatured state when exposed to heat. Furthermore, by adding a small amount of a surfactant containing fluorine atoms to the plasticizer, it is possible to coat the layer more uniformly, and the specific surfactant prevents other surfactants from penetrating into the molded product. It turned out to be helpful. That is, an object of the present invention is to provide an interfacial modification composition, especially an antifogging agent composition, suitable for coating or kneading onto the surface of a synthetic resin molded article, and a synthetic resin film coated with or containing the same. It is in. Therefore, the gist of the present invention is (A) a plasticizer and (B) the general formula or [In the formula, R and R ₃ are each an alkyl group or an aryl group having 6 to 30 carbon atoms, R ₁ , R ₂ , R ₄ and R ₅ are each an alkylene group having 1 to 5 carbon atoms, m, n, p and q are m
+n and p+q each represent an integer of 1 to 12. ] The present invention relates to a liquid surface-modifying composition containing as main components an amide compound or amine compound represented by the following formula and (C) a surfactant having a fluorinated alkyl group, and a synthetic resin film coated with or containing the same. To explain the present invention in detail, the plasticizer which is an essential component of the composition of the present invention may be any liquid plasticizer used for synthetic resins, such as dibutyl phthalate, diheptyl phthalate, phthalate. Phthalic acid plasticizers such as dioctyl acid, diisodecyl phthalate, butyl lauryl phthalate, ditridecyl phthalate, butyl benzyl phthalate, butyl phthalyl butyl glycolate, trimellitic acid plasticizers such as tributyl trimellitate, trioctyl trimellitate, pyromellitate Pyromellitic acid plasticizers such as tetrabutyl acid, tetraheptyl pyromellitate, phosphate plasticizers such as tricresyl phosphate, trioctyl phosphate, tributyl citrate, dibutyl adipate, dioctyl adipate, dioctyl azelaate, dibutyl sebacate, Examples include fatty acid plasticizers such as dioctyl sebacate, dibutoxyethyl sebacate, dimethyl sebacate, and methyl acetyl ricinoleate, and epoxy plasticizers such as alkyl epoxy stearate, which may be used alone or in combination. It is used by mixing. A secondary plasticizer such as epoxidized soybean oil or chlorinated paraffin can also be used in combination. Among these, phthalate plasticizers and fatty acid plasticizers easily penetrate from the surface of synthetic resin molded products into the interior, and dibutyl sebacate is particularly superior from the perspective of penetration, and is compatible with all thermoplastic resins. Dimethyl sebacate is good if you only consider the fact that it has General formula used in the composition of the invention In the structural formula of the amide compound represented by R, R is an optionally branched alkyl group or aryl group having 6 to 30 carbon atoms (hereinafter referred to as "C ₆ to ₃₀ "), especially an aryl group. It is preferably a _C8-22 alkyl group or aryl group, and the alkyl group or aryl group refers to a group having a double bond, a nitrogen atom, an oxygen atom, or a sulfur atom in its carbon atom chain _. shall be included. R ₁ and R ₂ are C _1
-5 , preferably an alkylene group which may have a _C2-4 branched chain, and _R1 and _R2 may be the same or different _. Moreover, it is preferable that m+n is an integer of 1 to 12. The number of carbon atoms in R is preferably determined by the number of carbon atoms in R ₁ and R ₂ or the number m+n. If it is too large, the permeability from the surface to the inside of the molded product tends to decrease, and Not the point. The number of carbon atoms in R ₁ and R ₂ is m+n
Although it depends on the number, it is preferably within the above range in consideration of antifogging properties, antiblocking properties, etc. Specific compounds include, for example, N-hydroxyethylheptylamide, N-hydroxyethyloctylamide, N-hydroxyethyldodecylamide (lauric acid), N-hydroxyethyloctadecylamide (stearic acid), N-hydroxyethyl Monoalkylolamides such as docosylamide, N-hydroxypropyldodecylamide, N-hydroxypropyloctadecylamide, N,N-di(hydroxyethyl)octylamide, N,N-di(hydroxyethyl)octadecylamide, N- Hydroxyethyl-N-hydroxypropyl octadecylamide, N,N-di(hydroxyethyl)-9-octadecenylamide (oleic acid), N,N-di(hydroxyethyl)-1-methylheptylamide, N, N-di(hydroxyethyl)tolylamide, N,N-
Addition of 1 to 12 moles of a C ₁ to ₅ alkylene oxide such as ethylene oxide or propylene oxide to a dialkylolamide such as di(hydroxyethyl)cyclohexylamide, or an alkylamide or arylamide such as dodecylamide, octadecylamide, benzamide, etc. Examples include polyoxyalkylene alkylamides or polyoxyalkylene arylamides such as polyoxyethylene alkylamides and polyoxypropylene alkylamides, and one type or a mixture of two or more of these may be used. In particular, N,N-di(hydroxyethyl)alkylamides are suitable for improving the anti-fogging and anti-blocking effects. However, the amount of the amide compound to be used cannot be determined unconditionally depending on the type of plasticizer, the type of synthetic resin to be kneaded or the molded product to be coated, the intended use, and the properties of the amide compound, but usually 100% of the plasticizer is used.
0.5 to 200 parts by weight, preferably 1 to 200 parts by weight
In the range of 100 parts by weight. Also, the general formula In the structural formula, R ₃ is R, R ₄ and R ₅ of the above-mentioned amide compound.
Similarly, R ₁ and R ₂ have the same meaning.
Although p+q also has the same meaning as m+n described above, it is particularly preferable that p+q is in the range of 2 to 6, and that p and q are each 1 or more. Specifically, amine compounds include monomers such as N-hydroxyethyldodecylamine, N-hydroxypropyldodecylamine, N-hydroxybutyldodecylamine, N-hydroxyethyloctadecylamine, and N-hydroxyethyloctadecenylamine. alkylolamine,
N,N-di(hydroxymethyl)dodecylamine, N,N-di(hydroxyethyl)dodecylamine, N,N-di(hydroxypropyl)dodecylamine, N,N-di(hydroxyethyl)octadecylamine, N, Dialkylolamines such as N-di(hydroxyethyl)octadecenylamine, N-hydroxyethyl-N-hydroxypropyloctadecylamine, or alkyl or arylamines such as dodecylamine, octadecylmine, aniline, benzylamine, etc. There are polyoxyalkylene alkylamines or polyoxyalkylene arylamines obtained by adding alkylene oxides such as ethylene oxide and propylene oxide in an amount of 1 to 12 moles, preferably 2 to 6 moles, and these can be used alone or in combination. A mixture of the above is used. However, the amount of the amine compound to be used cannot be determined unconditionally like the amide compound;
Usually 0.5 to 200 parts by weight per 100 parts by weight of plasticizer,
Preferably, the amount may be 1 to 100 parts by weight. The composition of the present invention is one in which the above-mentioned amide compound or amine compound is added to a plasticizer,
The amide compound or the amine compound may be used alone, or both may be used in combination. Since the composition may be heated after being applied, it is rather preferable to use both in combination from the viewpoint of thermal stability.
When both are used together, the amount of amide compound and amine compound used is 0.5 in total per 100 parts by weight of plasticizer.
It is sufficient that the amount is in the range of ~200 parts by weight. In particular, in order to fully exhibit the anti-fogging and anti-blocking effects, the ratio of the amide compound used is greater than the ratio of the amine compound, for example, preferably 20 parts by weight than the amount of the amine compound used. Use ~150% more. The composition of the present invention contains an amide compound or amine compound in order to apply it uniformly to the surface of a molded product and to promote the penetration and diffusion of the amide compound or amine compound into the synthetic resin during kneading. Additionally, a surfactant having a fluorinated alkyl group is added. By adding this, the surface tension of the composition is significantly lowered, and the composition can be uniformly spread over the surface of the molded article during application. The chemical structure of the surfactant includes, for example, fluoroalkyl carboxylates (alkali metal salts, alkaline earth metal salts, amine salts), perfluoroalkyl carboxylates, fluoroalkyl phosphate ester salts, perfluoroalkyl phosphate ester salts. , polyoxyethylene・
Perfluoroalkyl phosphate salts, perfluoroalkyl sulfate salts, polyoxyethylene perfluoroalkyl sulfate salts, perfluoroalkyl sulfonamide derivatives, perfluoroalkylamine salts, perfluoroalkyl quaternary ammonium salts, perfluoroalkyl imidazolines derivatives, perfluoroalkyl betaine, polyoxyethylene perfluoroalkyl ether, polyoxyethylene perfluoroalkyl phenol, polyoxyethylene perfluoroalkylamine, perfluoroalkyl carboxylic acid sorbitan ester, etc., among which fluorinated alkyl The number of carbon atoms in the group is not particularly limited, but is particularly 6 to 22.
It is preferred to use a range of . Specific examples include 16-fluorohexadecylcarboxylic acid, perfluorooctylcarboxylic acid N,N-diethanolamine, perfluorooctyl sodium phosphate, perfluorodecyl sodium phosphate, polyoxyethylene perfluorooctyl sodium phosphate, N -Polyoxyethylene-
N-ethyl perfluorooctyl sulfonamide,
N,N-di(polyoxyethylene) perfluorooctyl sulfonamide, N-polyoxyethylene-N-butyl perfluorodecyl sulfonamide,
N-polyoxyethylene-N-ethyl perfluorooctadecyl sulfonamide, perfluorodecyl trimethylammonium salt, perfluorooctadecyl-N-ethyldimethylammonium salt, perfluorooctadecyl betaine, polyoxyethylene perfluorooctyl ether, polyoxyethylene perfluorooctyl ether Various compounds such as fluorooctadecenyl ether, polyoxyethylene perfluorohexylamine, and perfluorododecylcarboxylic acid sorbitan ester are used. Among these, perfluoroalkyl phosphate esters and perfluoroalkyl sulfonamide derivatives are preferably used because they have a strong ability to transfer amide compounds and amine compounds from the surface of the molded article to the inside. Therefore, the amount of the surfactant having a fluorinated alkyl group is not particularly limited, but
It is usually used in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 2 parts by weight, per 100 parts by weight of plasticizer, depending on the type of surfactant, the purpose of the molded product, etc. Another aspect of the present invention is a surface-modified synthetic resin film in which the above-mentioned interface-modified composition is applied to the surface of the synthetic resin film. In the present invention, the synthetic resin film refers not only to films with a thickness of 0.3 mm or less, but also to films with a thickness of 0.3 mm or more, which are usually called sheets. The synthetic resin film is
It may be soft or hard, and is usually manufactured from thermoplastic resin by a molding method such as extrusion molding, calender roll molding, or inflation molding. The interfacially modified composition is applied to the surface of a synthetic resin film in a molten state or in a cooled state before being wound up into a roll during the film forming process of various molding methods. preferable. As a coating method, a spraying method, a roll coater method, a brushing method, a dipping method, or any other suitable method can be adopted depending on the film manufacturing process. If the coating is applied after cooling, it is preferable to heat it slightly and then wind it up. The surface-modified composition of the present invention may be kneaded into a synthetic resin and formed into a synthetic resin film with a surface modified. The film is produced by adding an interfacially modified composition to a synthetic resin, kneading the mixture uniformly, and then molding the mixture in the same manner as described above. However, the amount of the interfacially modified composition added to the synthetic resin depends on the type of synthetic resin, the amount of various auxiliary agents such as plasticizers and stabilizers added to the synthetic resin, and the composition of the interfacially modified composition. Cannot be determined, but usually synthetic resin
A suitable range is 1 to 70 parts by weight per 100 parts by weight. The film obtained by this method does not require the step of applying an interfacially modified composition after molding, which is advantageous in terms of work and economy. However, it has the disadvantage that it cannot achieve the effects of anti-blocking properties, anti-blocking properties, and anti-static properties. However, superficial effects are developed over time, and the effects can be exerted over a long period of time. Examples of thermoplastic resin agents used as raw materials for synthetic resin films include vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polystyrene,
ABS resin, acrylic resin, polyethylene, polypropylene, polyamide resin, acetal resin,
Polycarbonate, cellulose plastic, etc. are used, and vinyl chloride resin is most suitable because it has high utility as an agricultural film having antifogging properties. The vinyl chloride resin may be formed into a hard film, or may be formed into a film after being kneaded with a plasticizer. The surface-modified composition of the present invention uses a liquid plasticizer that is used in synthetic resins as a solvent for amide compounds or amine compounds that have excellent anti-fogging and anti-blocking effects, so it is easily compatible with synthetic resins. It is absorbed into synthetic resin without vaporizing. By the way, the critical surface tension of synthetic resin is
For example, vinyl chloride resin 39 dyne/cm, polyethylene 31 dyne/cm, polystyrene 33 dyne/cm, polymethyl methacrylate 39 dyne/cm, etc., while the surface tension of the plasticizer is, for example, dioctyl phthalate.
33dyne/cm, diisodecyl phthalate 29dyne/cm,
Butyl benzyl phthalate is 39.9 dyne/cm, dioctyl adipate is 29 dyne/cm, diisodecyl adipate is 30 dyne/cm, etc., and the surface tensions of the synthetic resin and plasticizer are similar. The interface modified composition is
If droplets form on the synthetic resin molded product during coating, adding a small amount of a surfactant having a fluorinated alkyl group will lower the surface tension of the composition, and it will spread evenly over the surface of the synthetic resin molded product. It spreads and promotes penetration of the composition, and exhibits interfacial modification effects, particularly antifogging, antiblocking, and antistatic properties, over a long period of time. The surface-modified composition of the present invention is coated on a synthetic resin film, especially a vinyl chloride resin film with excellent transparency, or is kneaded into a synthetic resin, especially a vinyl chloride resin, and then made into a film. It exhibits anti-fog effects over a long period of time, comparable to films that have been kneaded with additives. Synthesis imparted with antifogging agents such as fatty acid monoglycerides, fatty acid sorbiter esters, fatty acid polyglycerin esters, fatty acid trimethylolpropane esters, ethylene oxide adducts of fatty acids or polyhydric alcohol partial esters, or antifogging agents mixed with droplets. When the interfacial modification composition of the present invention is further applied to a resin film, the antifogging retention period is synergistically increased, and its utility value is extremely high. The present invention will be described in detail below with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. Example 1 (1) Film manufacturing method Film A mixed with an antifogging agent and Film B mixed with no antifogging agent were manufactured using the following formulation composition (parts by weight) and conditions.

[Table] Stell The above vinyl chloride resin composition was mixed uniformly using a Henschel mixer, then heated and kneaded using a kneader and a mill roll, and then formed into a 0.1 mm thick film using a calendar roll heated to 180°C. (2) Application of interface-modified compositions Make the following four interface-modified compositions (a) to (d).
Apply it evenly to one side of Film A and Film B using a reverse roll, and apply approximately
After passing through an air oven at a temperature of 100°C, the film was rolled up and used as data for an anti-fog property test. The resulting film had no stickiness from the plasticizer, and the plasticizer had penetrated into the inside of the film. (a) DOP 100 parts by weight N,N-dihydroxyethyldodecylamide
10 〃 N,N-dihydroxyethyldodecylamine
5 〃 Perfluorooctyl phosphate ester salt 0.01 〃 (B) DOP 100 〃 N,N-dihydroxyethyldodecylamide
15 〃 Perfluorooctyl phosphate ester salt 0.01 〃 (C) DOP 100 〃 N,N-dihydroxyethyldodecylamine
15 〃 Perfluorooctyl phosphate ester salt 0.01 〃 (d) DOP 100 〃 N,N-dihydroxyethyldodecylamide
10 〃 N,N-dihydroxyethyldodecylamine
5 〃 N-polyoxyethylene-N-ethyl perfluorooctylamide 0.01 〃 (3) Test method and results Anti-fog test Pour 10 liters of water into a bucket-like container of approximately 20 liters, and cover the coated surface with each sample material. The container was covered and sealed on the inside, and the container was held tilted due south at 30° to allow reflux of evaporated water. The test started in August last year, and the state of water droplet adhesion on the film was visually observed after 13 months, and the antifogging properties were investigated, as shown in Table 1.

[Table] Film B without an antifogging agent coated with the composition of the present invention exhibits antifogging properties equal to or better than Film A incorporating an antifogging agent, and the amount of water droplets attached is also small. Further, the composition of the present invention applied to the film A mixed with an antifogging agent was refluxed without adhesion of water droplets even after 13 months, showing excellent antifogging properties. Example 2 (1) Film manufacturing method Films C and D were formed using the following formulation (parts by weight) in the same manufacturing method as in Example 1. The antifogging properties of these films were evaluated in the same manner as in Example 1 and are listed in Table 2.

[Table] For the above-mentioned surface-modified compositions, (a) to (d) of Example 1 were used.

[Table] Film C mixed with interfacial modified composition and antifogging agent
Film D, in which only the interfacially modified composition was kneaded,
The antifogging property is better than that of Film A (no film) containing only an antifogging agent. In particular, Film C, in which the interface-modified composition and antifogging agent were kneaded, remained refluxed without any water droplets attached even after 13 months, and had excellent antifogging properties.

Claims (1)

[Claims] 1 (A) Plasticizer, (B) General formula or [In the formula, R and R ₃ are each an alkyl group or an aryl group having 6 to 30 carbon atoms, R ₁ , R ₂ , R ₄ and R ₅ are each an alkylene group having 1 to 5 carbon atoms, m , n, p and q, n+m and p+q each represent an integer of 1 to 12. ] A liquid surface-modifying composition containing as main components an amide compound or amine compound represented by the following formula and (C) a surfactant having a fluorinated alkyl group. 2 (A) Plasticizer, (B) General formula or [In the formula, R and R ₃ are each an alkyl group having 6 to 30 carbon atoms or an aryl group, R ₁ , R ₂ , R ₄ and R ₅ are each an alkylene group having 1 to 5 carbon atoms, m , n, p and q, n+m and p+q each represent an integer of 1 to 12. ] (C) A synthetic resin film coated with an interfacial modification composition whose main component is a surfactant having a fluorinated alkyl group. 3. The synthetic resin film according to claim 2, wherein the synthetic resin is a vinyl chloride resin. 4 (A) Plasticizer, (B) General formula or [In the formula, R and R ₃ are each an alkyl group or an aryl group having 6 to 30 carbon atoms, R ₁ , R ₂ , R ₄ and R ₅ are each an alkylene group having 1 to 5 carbon atoms, m , n, p and q, n+m and p+q each represent an integer of 1 to 12. (C) A synthetic resin film formed by kneading a surface-modified composition containing a surfactant having a fluorinated alkyl group as a main component into a synthetic resin. 5. The synthetic resin film according to claim 4, wherein the synthetic resin is a vinyl chloride resin.