TWI364444B - Acryloxy-functional silicone composition curable by high-energy radiation - Google Patents

Description

[04444] Nine, the invention relates to: [Technical field of the invention] The present invention relates to a propyleneoxy-functionalized vanadium-oxygen composition which can be hardened by high-energy radiation, characterized in that the composition has excellent storage stability and It is suitable for the formation of hardened coatings which have been proven to have improved scratch resistance, transparency, water repellency and adhesion. [Prior Art] A conventional coating agent which can be lightly hardened when exposed to an ultraviolet 'wire, an electron beam, a read line or the like, can include - a composition consisting of polyfunctional acrylic acid s胄 'Amino functional decyloxy and ruthenium dioxide (see European Patent No. 687713, European Patent No. 66629 、, European Patent No. 437327) or a combination of diacrylate and amine modified The Michael addition reaction product of the oxime-burning (see U.S. Patent No. 4,6,3, 〇86, the entire disclosure of which is incorporated herein by reference. However, the above-mentioned λ first-mentioned coating agent comprising an amine functional group & oxy-stone and a gelatin dioxide is easy to gel and stable in storage, and the diacrylate and the latter are mentioned. The addition reaction product of the amine-modified polyoxyalkylene has low scratch resistance when formed into a cured film. SUMMARY OF THE INVENTION The present invention is directed to providing an acryloxy-functional polyoxo-oxygen composition which is hardenable by high-energy radiation, which is characterized by excellent storage stability and when hardened into a coating. Improved scratch resistance, transparency, water repellency and improved adhesion. The present invention relates to a cyanoxy functional group 95396.doc 1364444 4 sand oxide composition which can be light-hardened by high energy, which comprises: (A) at least one polyfunctional acrylate; (B) - modified by an amine group a polyorganosiloxane having a lower molar amount of an amine group in component (B) than a mole of an acrylate functional group in component (A); (c) an organic having an aliphatic unsaturated bond Alkoxy decane; (D) - colloidal cerium oxide; and (E) - an organic solvent containing an alcohol. Further, the present invention relates to an acryloxy-functional polyoxyl composition which is hardenable by high-energy radiation, comprising: (A) at least one polyfunctional acrylic acid vinegar; (F) (A) at least one polyfunctional a product of a acrylic acid ester-addition reaction with (B) an amine-modified polyorgano-zeitocene; (C) an organoalkoxydecane having an aliphatic unsaturated bond; (D)- Colloidal cerium oxide; and (E) - an organic solvent containing an alcohol. [Embodiment] The component (A) can impart a cleavage of a composition of the present invention which can be hardened by irradiation, and includes an acrylate having two or more functionalities. The following are specific examples of compounds suitable as component (A): hydrazine, 6-hexanediol dipropylene hydrazine, 1,4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol Alcohol-acrylic acid vinegar, tetraethylene glycol diacrylate, tripropylene glycol diacrylic acid S hydrazine, neopentyl glycol diacrylate, hydrazine, 4-butanediol dimercapto acrylate, poly(butylene glycol) diacrylate , tetraethylene glycol dimercapto acrylate, hydrazine, 3 - butanediol dipropylene vinegar 'triethylene glycol diacrylate, triisopropyl glycol dipropylene 95396.doc 1364444 acid ester, polyethylene glycol two Acrylate, bisphenol A dimethacrylate, or a similar difunctional acrylate monomer; trimethylolpropane tripropionate, trimethylolpropane tridecyl acrylate, pentaerythritol single Hydroxyl methacrylate, bis-decyl propyl triethoxy dipropionate, or a trifunctional acrylate monomer; pentaerythritol tetrapropyl acrylate Benzene tetraacrylate, or a similar tetrafunctional acrylic acid monomer; diisodecyl alcohol hexaacrylate, diisoamyl Yeast (monohydroxy) pentaacrylate, or a five similar or acrylate monomers of higher functionality. A polyfunctional acrylate-based polymer can also be used and can be represented by the following specific examples: bis, phenol A epoxy acrylate Ss, hexafunctional aromatic urethane acetoacetate [trade name: Ebecryl 220 / UCB Chemicals, Inc., Aliphatic urethane diacrylate [trade name: Ebecryl 230/ UCB Chemicals] and tetrafunctional polyacetate acrylate [trade name: Ebecryl 8〇 / UCB Chemicais]. The above polyfunctional acrylates may be used singly or in combination of two or more kinds. The above preferred ones are acrylates of five or higher functionality. The amount of such acrylic vinegar should be greater than 3 〇 wt % of the component, preferably greater than 50 wt.%, and even more preferably greater than 80 wt %. Component (B) imparts properties such as water repellent and full slip properties to the hardened coating obtained from the composition of the present invention. The component is a polyorganosiloxane stream having an amino functional organic group at its molecular end and partially on the molecular side chain. The above amino functional organic group may be represented by 2-aminoethyl, 3-aminopropyl, 3-(2-aminoethyl)aminopropyl and 6-aminohexyl. A group other than an amine functional organic group may also be used and may be represented by the group: methyl, ethylpropyl or the like; phenyl or similar 95396.doc 1364444 square , methoxy, ethoxy, propoxy or similar alkoxy, and trans. The best of the descriptions, methyl. The polyorgano oxy-oxygenation as component (8) may be a linear or partially branched linear structure. The degree of polymerization of the polyoxygen is between 2 and 1000', preferably 2 to 5, and even more preferably 2 to 300. An example of the component (8) may include a polyorganosopene which mainly contains an amine group and is represented by the following formula. In this equation, Me represents a methyl group. NH2C3H6.Me2S i 〇 (me S Γ Γ)Ί q · A/r

^ vme2b i 1〇s iMe2-C3H6NH2 Me M e Me NH2C2H4NHC3H6-S i〇 (s iO) 6S i-C3H6NHC2H4NH2

Me Me Me

Me3S !〇 (Me2S i 〇) 5〇 (M e S i 〇) 6s iMe3

I C3H6NH2

Me3S iO (Me2S iO) 8〇 (MeS i〇) i〇s iMea

I c3h6nhc2h4nh2 It is recommended to use the component (B) in an amount such that the molar amount of the total amine group of the supplied component (B) is less than the molar amount of the acrylic acid acrylate functional group of the component (A). It is preferred that the weight of the component (B) is less than the weight of the component (A). Component (F) is the reaction product between the acrylate functional group of the above component (A) and the amine group of the component (B) which has also been described above. Component (C) is an organoalkoxy decane having an aliphatic unsaturated bond. Component (c) may improve the affinity between component (D) colloidal ceria and component (A) 95396.doc 1364444 or component (B) and when component (c) is used to treat the component ( The surface of D) imparts improved storage stability to the composition. During hardening, component (C) reacts with component (A) and thereby increases the degree of crosslinking of the hardened product. The group having an aliphatic unsaturated bond used in the component can be exemplified by 3-(methacryloxy)propyl, 3-(propyleneoxy)propyl or similar propylene-containing organic groups. a group; a vinyl group, an allyl group or an alkenyl group. The alkoxy group can be represented by a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The above component (c soil) can be exemplified by 3-(methacryloxy)propyltrimethoxy decane, 3-(mercapto propyleneoxy)propyltriethoxy decane, 3•(A) Propyloxy)propylmethyldimethoxydecane, 3-(propyleneoxy)propyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, methylethylenediyl Methoxy oxime and allyl triethoxy oxalate. Component (D) is a colloidal cerium oxide. Component (D) is used to increase the hardness and scratch resistance of the coating obtained by hardening the composition of the present invention. The component may comprise a colloidal ceria which is dispersible in water, an alcohol or an organic solvent. It is recommended that the average particle diameter of the colloidal ceria is between several nanometers and several tens of nanometers, and the component (E) is an organic solvent containing an alcohol. Examples of alcohols of the following components (£): decyl alcohol, ethanol, isopropanol, butanol, isobutanol, ethylene glycol, diethyl alcohol, diethylene glycol, ethylene glycol monomethyl ether, diethyl Glycol monomethyl ether and triethyl alcohol monoterpene ether. The following organic solvents can be used in addition to alcohol: propional, methyl ethyl ketone, methyl isobutyl ketone or similar ketone; methyl, xylene or similar aromatic hydrocarbons, hexane, octane, heptane or Similar to aliphatic hydrocarbons; gas imitation, di-methane methane tri-ethylene, tetra-carbonized carbon and similar chlorine-containing organic solvents; acetic acid 95396.doc 1364444 ethyl ester, butyl acetate, acetic acid succinct * & diced lg or similar Fatty acid esters. The component (£) may comprise only alcohol or a mixture comprising an alcohol and another solvent. The composition may comprise an alcohol and two or more different types of solvents. The amount of the alcohol may be from 10 to 90% by weight based on the total weight of the solvent, preferably from 3 to 7 % by weight. Although the content of each component is not particularly limited except for the component (B), it is recommended that the amount of the component W and the component (C) is 1 for each part by weight of the component (A). Up to 30 parts by weight, preferably α2〇 parts by weight. The amount of the component (9) should be H 〇〇 weight damage per part by weight of the array (4), preferably from 1 to 80 parts by weight. The amount of the component (Ε) should be from 1 to 1 part by weight, preferably from (7) to 5 parts by weight, per part by weight of the (8) parts by weight of the 份. The component (F) is used in an amount of from 1 to 100 parts by weight, preferably from 1 to 5 parts by weight, per 1 part by weight of the array (α). Optionally, the compositions may also include a component for hydrolysis (water (component (G)). For each 100 parts by weight of component (c), 1 to 5 parts by weight may be added. 'and the wound (G)' is preferably 5 to 30 parts by weight. Usually, the component (c) is reacted with the stanol group on the surface of the colloidal cerium oxide as the component (D) and is component (G). Hydrolysis. Therefore, the amount of component (G) may be less than the amount required for the hydrolysis of the entire component (c). If hardened by ultraviolet radiation, the propyleneoxy functional polyoxyl composition of the present invention may comprise at least A photopolymerization initiator The photopolymerization initiator may include, for example, 2-methyl-{4-(methylthio)phenyl}_2_fofofyl-propane (a product of Chiba-Geigy Japan, Registered trademark: iRGACURE 9〇7) and 1-base based base (chiba-GeigyJapan product, trade name: IRGACURE 1 84®). Benzophenone, acetophenone, benzoin, or 95396.doc t, Various benzoin derivatives and other suitable photopolymerization initiators can be used for the same purpose. They can be used singly or in combination of two or more. Photo-water. Starting β. There is no particular limitation on the amount of the component (8) in the composition of the present invention, but usually it is added in an amount of from 1 to 3 g by weight per (10) parts by weight of the array (α). Preferably, it is 120 parts by weight. The composition of the present invention may contain various additives, for example, tetramethoxy (tetra), tetraethoxy (tetra), tetra (isopropoxy), within the scope not departing from the object of the present invention. ) 夕 烧 or similar four-yard oxydecane; methyl trimethoxy decane, methyl monoethoxy decane, decyl tris (isopropoxy) decane, ethyl tridecyl decane, ethyl three Ethoxy decane, ethyl tris(isopropoxy) decane or similar alkyl alkoxy decane. Right, the composition of the present invention may also contain a thickener; a UV absorber; various pigments, dyes or the like. Colorant; aluminum paste, talc, glass frit, metal powder, etc., dibutyl hydroxy hydrazine (BHT), thiodiphenylamine (ρτζ) or similar acrylate type self-polymerization inhibitor, or other additives. The method for inventing the composition is not particularly limited, and the hanging is carried out. It is recommended to mix uniformly by mixing. In this case, it is recommended to first react the components (Α) with (Β) and then add other components. Since the amount of the amine group of the component (Β) is larger than the component (Α) The molar number of the acrylate functional group is small, so after the reaction of the component (A) with the component (B) is completed, a mixture of the unreacted portion of the component and the component (F) is subsequently prepared, wherein the group The fraction (ρ >) is a product of the Michael addition reaction of the components (A) and (B). For example, the composition of the present invention can be obtained by the following methods (A) and (B) (E) In the middle of the reaction to prepare: Mix the components (A), (B) and 95396.doc • 12 ' 1364444 (E) at a temperature between room temperature and the reflux temperature of the solvent for 1 minute to 2 hours, then add Component (c) and (D) and, if necessary, component (G)' and continue mixing for a further 1 minute to 20 hours at a temperature between room temperature and solvent reflux temperature. Alternatively, the composition can be prepared by reacting components (A) and (B) in component (E) by reacting the component at a temperature between room temperature and the reflux temperature of the solvent (A). And (8) and (E) are mixed for 1 minute to an hour, and the product is combined with a mixture obtained by mixing the mixture (G) with the components (c) and (D), or This product is combined with a mixture of components (c), (D) and (1)), and the obtained mixture is mixed for a period of 2 minutes to 2 hours at a temperature between room temperature and the reflux temperature of the solvent. After cooling, the component (H) can be added and mixed. The compositions of the present invention can be applied to a variety of substrates, dried, and then hardened in a very short period of time by exposing them to a radiant energy. The radiant energy can include ultraviolet radiation, electron beams, gamma rays, or the like. In the case of ultraviolet radiation, a hardened thin coating can be formed in a very short exposure time. It is recommended that the amount of radiation be not less than 2 mj/cm2, preferably between 1 〇 and 2 〇〇〇 mJ/cm2. If hardening is performed by electron beam or gamma rays, it may not be necessary to add a component (Η). Although the composition of the present invention can be dried at room temperature, the drying process can be accelerated by heating. There is no particular limitation on the substrate suitable for applying the composition of the present invention. For example, the substrate can be made of polyethylene, polypropylene, or similar polyolefin-type resin; polyethylene terephthalate, polyethylene glycol diester, poly 2, 6 - ethylene naphthalate, polybutylene dibutanoate, copolymers thereof or similar polyester resins; polyfurfural or similar polyamine resins; polystyrene, poly(methyl) Acrylate, polyacrylonitrile, polyvinyl acetate, 95396.doc 13 444 444 K 厌 文 文 曰 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇

Plastic resin, melamine resin, polyurethane resin, epoxy resin, ionic resin, fluororesin or a similar heat, alkyd resin, urea resin, poly. The form of the substrate is not particularly limited, and is made of a sheet, a bottle, a solid body or a similar phenolic resin, an unsaturated polyester resin, or a thermosetting resin, and the substrate form may include a film. A thermoplastic film. The thickness of the substrate is not particularly limited, but is preferably between 5 and 100 μm for the film or sheet. The composition of the present invention can be applied to a substrate in a thin layer by any suitable method, including flow coating, dip coating, spin coating, spray coating, curtain coating, and gravure coating. And Meyei^〗 strip coating. Prior to application of the composition, the surface of the substrate can be subjected to a well-known activation treatment (e.g., corona discharge treatment) or a fixed treatment with a urethane resin. When it is desired to provide scratch resistance, the thickness of the layer is preferably between 〇 5 and 25 μm, more preferably 1 to 20 μm. After coating, the thin layer is dried and hardened. When the propyleneoxy functional polyoxyl composition of the present invention which can be hardened by high energy radiation is prepared from the above component (A) to, if necessary, and the additional component and (H), the composition can be provided. The storage stability provides improved scratch resistance, transparency, water repellency and adhesion in the hard cured coating prepared from the above group of materials. The invention will be elucidated below with reference to examples. In these examples, all parts are by weight and Me represents methyl. The viscosity value corresponds to the contact angle of the viscosity-hardened layer at 25 ° C with water measured by a CA-Z type automatic contact angle meter manufactured by Ky〇wa Kaimen Kagaku Co., Ltd. 95396.doc 14 1364444 Example 1: 52.3 g of toluene, 21 g of isopropanol (hereinafter referred to as IPA) and 23.9 g of diisopentyltetraol hexaacrylate (6 wt.%) and diisopentaerythritol ( A mixture of monohydroxy)pentaacrylate (4 〇 wt.%) (content of acrylate functional group: 0.24 mole) was filled into a flask and the components were stirred. Thereafter, 1.49 g was added with the following An amine-modified polydimethyloxane fluid of the average molecular formula (amine content: 〇.〇〇1 mol) was obtained, and the mixture was heated and stirred at 5 (TC) for 1 hour.

Me3S i 〇 (Me2S i O) 235 (Me S i O) 15S i Me3

I c3h6nhc2h4nh2 Thus, a reaction mixture was prepared. The product was sequentially stirred with 3.74 g of 3-methylpropoxypropyltrimethoxysulfonate, 44.9 g of a colloidal ceria IPA dispersion (concentration: 3 〇 wt%; average particle size of colloidal cerium oxide particles) : 13 nm) and 0.46 g of water were mixed and the ingredients were stirred for 1 hour. After the mixture was cooled, 2 25 g of a photopolymerization initiator (product of Chiba-Geigy Japan, registered trademark: irgacure 184) and 4.5 mg of thiodiphenylamine were added. The obtained product contained a propyleneoxy functional polyoxyl composition A. The composition had a melt viscosity of 3 mm 2 /s and remained substantially unchanged after storage for 6 months. Therefore, it can be concluded that the composition A has good storage stability. The obtained composition A was applied onto a 188 μm thick PET film by a bar coater at 12 Torr. The coating was dried under the arm for 2 minutes. Then, the coating was hardened by exposure to ultraviolet radiation having a strength of 350: Thus, a thin film of 95396.doc • 15-1364444 coated with a coating of a 2 μm thick hardening composition was prepared. The hardened thin coating had a water contact angle of 98. And the pencil hardness is 3h. No oil bleed was observed. After the obtained coated PET film was allowed to stand at room temperature for one month, a race tape was adhered to the surface thereof to carry out a peeling test on the coating (peeling rate: 1 mm/min, angle 180). ). The coating was not peeled off and it remained firmly adhered to the PET film. Moreover, when the surface of the film is rubbed with steel wool, there is substantially no scratch. The transmittance of the PET film obtained by measuring the transmittance (55 Å nanometer) of the PET film was measured by a UV-visible spectrophotometer (Shimacjzu's uv-visible self-recording spectrophotometer, UV-265FW). This transmittance is even higher than that of an untreated PET film. In other words, assuming that the transmittance of the untreated film is 1%, the properties of the coated film are increased to 104%. The rubbing test carried out on the Taber abrasion tester (friction load 5 gram and the grinding wheel was 1 turn) did not change the light transmittance of the coated film, that is, the transmittance remained the same after re-measurement. The degree is 104%. Example 2: 52.3 g of toluene, 21 g of IPA and 23.9 g of diisopentyltetraol hexaacrylate (60 wt.%) and diisopentaerythritol (monohydroxy) pentaacrylate (4 〇 wt. ° / 〇 A mixture of acrylate functional groups (〇24 mol) was filled into a flask and the components were stirred. Thereafter, 1 g of an amine-modified polydimethyloxane fluid (amine content: 0.002 mol) having an average molecular formula shown below was added, and the mixture was heated at 5 Torr. (: Mixing for 1 hour. NH2C3H6-Me2SiO(Me2SiO)9SiMe2-C3H6NH2 was prepared as a reaction mixture. This product was sequentially and 3.7 g of 3-methylpropoxypropyltrimethoxy oxylate 95396.doc • 16· gram of colloidal cerium oxide IPA dispersion (concentration: 3 〇 wt%; plastic 'average particle size of the dioxide dioxide granules: 13 nm) and 〇 46 grams of water mixed, and 乂 乂 for half an hour. The mixture is cooled &, adding 2 25 grams of light

1 starter (Chiba-Geigy japan product, registered trademark: IRGACURE 184) and 4.5 mg thiodiphenylamine. The obtained product contained a propyleneoxy functional polyoxyl composition B. The obtained composition B was applied to an i micron thick PET film by a bar coater, and after exposure to a thickness of 350 mJ at 12 minutes after drying the coating. The coating is hardened by ultraviolet radiation of /cm2. This film is coated with a PET film coated with a 2 μm thick hardening composition b. » The water contact angle of the thin hard layer is 1 〇〇, and the hardness of the wrong pen is After the obtained coated PET film was kept at room temperature for one month, the coating was subjected to a peeling test by the same method as described in Example 1. The coating was not peeled off and it was still Firmly adhered to the PET film. And 'When the surface of the film layer was rubbed with steel wool, there was substantially no scratch. The transmittance of the obtained PET film was measured by the same method as in Example 1 (550 nm) The transmittance was 丨〇5% and improved compared with the untreated PET film. The surface of the hardened coating was measured using a portable friction tester (product of Tritog Kagaku Co., Ltd. 'Tribogear-Muse type 941) Static friction coefficient 'the coefficient of static friction is equal to 0.17 ps, compared to the untreated film The coefficient of static friction of the surface (0.19 ps) was improved. Example 3: 21 g of toluene, 52 g of IPA and 24 g of diisopentaerythritol hexaacrylate S (60 wt.%) and diisopentaerythritol (single basis) vinegar vinegar (4〇95396.doc 17 1364444

A mixture of Wt.%) (content of acrylate functional group: 0.24 mole) was filled into a flask, and the components were stirred. Thereafter, 3 g of an amine-modified polydimethylsiloxane (the amine group containing 1 · 0.001 mol) having the average molecular formula given below was added, and the mixture was heated and mixed at 5 〇 «» C 1 hour. NH2C3H6.Me2SiO(Me2SiO)5〇SiMe2-C3H6NH2 Thus, a reaction mixture was obtained. The product was sequentially mixed with 3.7 g of 3-methylpropoxypropyltrimethoxy oxalate, 45 g of a colloidal cerium oxide IpA dispersion (concentration: 3 〇 wt%; average particle size of colloidal cerium oxide particles) : 13 nm) and 46 g of water were mixed and the ingredients were stirred for a few hours. After the mixture was cooled, 2 25 g of a photopolymerization initiator (product of Chiba-Geigy Japan, registered trademark: IRGAcuRE 184®) and 4.5 mg of thiodiphenylamine were added to obtain a product containing a propyleneoxy functional group. Object C. The obtained composition C was applied to a film of 88 μm thick PET film using a bar coater, and the coating was dried under 12 Torr for 2 minutes. The coating was then hardened by exposure to ultraviolet radiation having an intensity of 350 mJ/cm2. This produced a PET film coated with a 2 μm thick hardened composition c coating. The hardened thin layer has a water contact angle of 99. And the pencil hardness is 3H. After the obtained coated PET film was kept at room temperature for one month, the coating was subjected to a peeling test by the same method as described in Example 1. The coating was not peeled off and it remained firmly adhered to the ΡΕτ film. Moreover, when the surface of the film layer is rubbed with steel wool, there is substantially no scratch. The transmittance (550 nm) of the obtained PET film was measured by the same method as in Example 1. The transmittance was 1〇3% and was improved from the untreated pet film phase 95396.doc -18-1364444. The static friction coefficient of the surface of the hardened coating was measured by the same method as described in Example 2 and was equal to 0.11 μ5, which was improved over the static friction coefficient (0·19 ps) of the surface of the untreated film. Example 4: 52.3 g of toluene, 21 g of IPA and 23.9 g of diisopentyltetraol hexaacrylate (60 wt.%) and diisopentaerythritol (monohydroxy)pentaacrylate (4 〇 wt.%) The mixture (content of acrylate functional group: 〇·24 mol) was filled into a flask, and the components were stirred. Thereafter, 149 g of an amino group-modified polydidecylhydroxane fluid (amine group a 1 〇.〇〇 1 mol) having an average molecular formula given below was added, and the mixture was heated at 5 Torr. Underarms search for hours.

Me3S 1 〇 (Me2S i O) 235 (Me S i 〇) 15S i Me3

I c3h6nhc2h4nh2 Thus, a reaction mixture was prepared. The product was sequentially mixed with 3.94 g of 3-methylpropoxypropyltrimethoxydecane 44.9 g of a colloidal cerium oxide IPA dispersion (concentration: 3 〇wt 〇 / 〇; average particle size of colloidal cerium oxide particles) : 13 nm) Mix and mix the ingredients for 1 hour. After the mixture was cooled, 2 25 g of a photopolymerization initiator (product of Chiba-Geigy Japan, registered trademark: irgacure (8) 8) and 4.5 mg of thiodiphenylamine were added. The obtained product contained a propyleneoxy functional polyoxyl composition. D. The obtained composition D was applied onto a 88 μm thick PET film by a bar coater, and the coating was dried at 12 ° C for 2 minutes. Then, the coating was hardened by ultraviolet rays under ultraviolet radiation having an intensity of 350 mJ/cm2. 95396.doc 1364444 A pet film coated with a 2 micron thick hardened composition D coating was prepared. The hardened thin layer has a water contact angle of 97. And the pencil hardness is 3H. Not observed. To oil oozing. Moreover, when the surface of the film layer is rubbed with steel wool, the base has no scratches. Comparative Example 1: A propyleneoxyg-month b-based composition was prepared by the same method as in Example 1, except that 3 74 g of 3-methacryloxypropyltrimethoxysulfene was not added thereto. The composition obtained had white turbidity and a white precipitate appeared after 1 month of storage. From this, it can be inferred that the storage stability of the composition is not high enough. m Comparative Example 2: 52.3 g of terpene, 21 g of IPA and 23.9 g of diisopentyl alcohol octapropylene from 酗 (60 wt·%) and diisopentaerythritol (monohydroxy) pentaacrylate (4 〇wt The mixture of .%) was filled into a flask and the components were stirred. Then, the IPA dispersion of the product of the product and the 3.74 g of 3-methylpropoxypropyltrimethoxydecane 44·9 g of a colloidal ceria (concentration: 30 wt.%; colloidal dioxygen) The average particle size of the cut pellets: 13 nm), 〇.46 g of water was mixed, and the children and other groups were stirred for an hour. After the mixture was cooled, 2 gram of light polymerization initiator (product of Chiba-Geigy Japan, registered trademark: IRGACURE 184®) and ketone diphenylamine were added. Obtained; — a propyleneoxy functional polyfluorene composition. The obtained composition was coated on a PET film by the method described in Example 1. The hardened thin coating has a water contact angle of 8 Å. It is believed that the coating does not have sufficient water repellency. · t匕Comparative Example 3. A propyleneoxy 'Lvyue b-based polyglycol composition was prepared by the same method as in Example i, except that the viscosity of 〇 2 g was 2 々 and at 95396.doc • 20- 1364444 molecular side chain with polyoxyethylene group (polyoxyethylene chain content: 47 μ polydimethyl methoxy hydride fluid instead of amine-modified polydimethyl methoxy hydride fluid. The obtained composition was applied to a PET film by the method described in Example 1. The hardened thin coating layer had a water contact angle of 90, and the coating was considered to have insufficient water repellency. There is an oil exudate on the surface of the hardened layer. The above composition of the present invention is characterized by excellent storage stability' while the product obtained by hardening the composition is characterized by high scratch resistance, transparency, water repellency, Adhesion, weather resistance and UV resistance. Therefore, the composition is suitable for use as an antimony agent and coating agent for coating various substrates. Pre-reaction of group injury (Α) and (Β) can prevent oil from self-reaction The coating bleeds out and prevents stability from diminishing over time. Compositions of the invention Some applications use in hardening of the film, such as' windows, construction glass, displays, touch panel, or protective film of a magnetic card; headlight glass or the like transparent resin.

95396.doc 21 -

Claims (1)

Patent Application No. 093125002 (IV) Year ^ Month, V Day Amendment This Chinese patent application scope is replaced by this (1〇〇ΨΤΓΚ) I3644MS X. Patent application scope: 1. A propylene oxy-functional group condensed by high-energy radiation hardening An oxygen composition comprising: (Α) at least one polyfunctional acrylate; (Β) - an amine-modified polyorganosiloxane having at least one selected from the group consisting of 2-aminoethyl, 3-amine An amino functional group organic group consisting of a group consisting of a propyl group, a 3-(2-aminoethyl)aminopropyl group and a 6-aminohexyl group, wherein the amount of the amine group in the component (B) is higher The amount of the acrylate functional group in the component (A) is small; (C) a spring organic alkoxy decane having an aliphatic unsaturated bond; (D) - colloidal cerium oxide; and (E) - Alcohol-containing organic solvent. 2. The propyleneoxy functional polyoxyl composition according to claim 1 which is hardenable by high energy radiation, wherein the content of the component (B) is 1 to 100 parts by weight of the array (A). 30 parts by weight, the content of the component (C) is 1 to 30 parts by weight, the content of the component (D) is 1 to 100 parts by weight, and the content of the component (E) is ίο to 1〇〇〇. Parts by weight. ® 3. A propyleneoxy functional polyoxyl composition which is hardenable by high energy radiation, comprising: (A) at least one polyfunctional acrylate; (F) - (A) at least one polyfunctional acrylate And (B) a product of a Michael addition reaction of an amine-modified polyorganooxyl, at least one selected from the group consisting of 2-aminoethyl, 3- Amino group i. propyl, 3-(2-aminoethyl)aminopropyl and 6-aminohexyl group 95396-1001209.doc D12547 95396 012709792-1 1364444 Group of amino functional organic groups; (c) an organoalkoxydecane having an aliphatic unsaturated bond; (D) - colloidal cerium oxide; and (E) - an organic solvent containing an alcohol. 4. The propyleneoxy functional polyoxyl composition according to claim 3, which is hardenable by high energy radiation, wherein the component (F) is in an amount of 1 to 100 parts by weight of the array (A). 100 parts by weight, the content of the component (C) is 1 to 30 parts by weight, the content of the component (D) is 1 to 100 parts by weight, and the content of the component (E) is 10 to 1000 parts by weight. . 5. The propyleneoxy functional polyoxyl composition according to claim 1 or 3 which is hardenable by high energy radiation, which further comprises (G) water for hydrolyzing component (C). ·····- , · , - 6. A high-energy radiation-hardenable propylene oxy-functional polyoxyl composition as claimed in claim 2 or 4, for each 1 part by weight of the array (C) In terms of it, it further includes '1 to 50 parts by weight of (G) water. 7. The propyleneoxy functional polyoxyl composition which can be cured by high energy radiation according to any one of claims 1 to 4, wherein the component (B) is less than the component (A) by weight. _1/5. 8. A propylene oxy-functional polyoxy oxy-compound composition which is curable by high energy radiation, according to any one of claims 1 to 4, wherein the component (A) is a acrylate having a 5% or higher functionality. 9. The propyleneoxy functional polyoxyl composition which is hardenable by high energy radiation according to any one of claims 1 to 4, which further comprises at least one photopolymerization initiator (H). 95396-1001209.doc