KR20140025626A - Environmental friendly urethane bonded link polysiloxane resin reinforced with reactive silane surface modified inorganic sphere particle and its manufacturing method - Google Patents
Environmental friendly urethane bonded link polysiloxane resin reinforced with reactive silane surface modified inorganic sphere particle and its manufacturing method Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G77/04—Polysiloxanes
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Abstract
Inorganic hollow particles composed of perlite, silica, alumina and titanium dioxide are heat-treated at 100 to 140 ° C to remove moisture or contaminants on the surface. Steps;
Aminosilane such as 20-40 parts by weight of 3-aminopropyl triethoxysilan or 3-isocyanatopropyl triethoxysilane in a reactor equipped with a stirrer and a condensation capacitor Silane which has reactive groups, such as isocyanate silane, 3-carboxypropyl triethoxysilane, such as carboxysilane, such as 3-carboxypropyl triethoxysilane, and 3-hydroxypropyl triethoxysilane; 60 to 80 parts by weight of an organic solvent such as heptane or toluene is added, and 20 to 40 parts by weight of heat-treated hollow particles obtained in the hollow particle heat treatment step are added while stirring at 40 to 60 rpm. A step of preparing hollow particles surface-modified with reactive silane which is reacted for a period of time and then filtered and dried in a vacuum oven at 40 to 60 ° C. for 12 to 48 hours;
80 to 99 parts by weight of the hollow particles surface-modified with 1 to 20 parts by weight of reactive silane prepared in the step of producing the hollow particles surface-modified with the reactive silane in a glass reactor (polyetherdiol or polyesterdiol) adding a polydiol such as (polyesterdiol) to disperse the surface-modified hollow particles in the polydiol for 1 to 2 hours at 20 to 80 ° C. in an ultrasonic bath;
20 to 60 parts by weight of a polydiol in which 100 parts by weight of surface-modified hollow particles prepared in the step of dispersing the surface-modified hollow particles in a polydiol in a reactor equipped with a thermometer, a stirrer and a condensation capacitor under nitrogen supply Isocyanate-terminated polydimethylsiloxane, 60-100 parts by weight of hexamethylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diisocyanato Low molecular weight diisocyanates such as dicyclohexyl methane (4,4'-diisocyanatodi cyclohexyl methane), tolyene diisocyanate, diphenyl methane diisocyanate, 5-20 parts by weight of hydrooxyacetic Hydroxyacetic acid, aminoacetic acid, lysine, N-2-aminoethyl-2-aminoethane sulfonic acid (N-2-aminoethyl-2-aminoethan e sulfonic acid), reactive organic acids such as 2,2-bis (hydroxymethyl) propionic acid] and 0.001 to 0.05 parts by weight of 1,4-diazabicyclo Polycondensation catalysts such as (2,2,2) octane [1,4-diazabicyclo (2.2.2) octane], dibutyl tin dilaurate, dibutyl tin maleate After the catalyst was added, the reaction temperature was increased to 100-120 ° C. and the urethane-linked linkage polysiloxane prepolymer was prepared by in-situ polymerization with the surface-modified hollow particles prepared by in-situ polymerization for 6 to 12 hours while stirring at 20 to 50 rpm. ) Manufacturing step;
5 to 25 parts by weight of polyethylene glycol diacrylate on the surface-modified hollow particles reacted urethane-linked link polysiloxane prepolymer prepared in the step of preparing the urethane-linked polysiloxane prepolymer reacted with the surface-modified hollow particles ( polymerization inhibitors such as difunctional diacrylates such as polyethylene glycol diacrylate) and 1,3-propanediol dimethacrylate and 0.1 to 0.5 parts by weight of hydroquinone and 0.001 to Introducing an ultraviolet curable group by adding 0.05 parts by weight of a condensation catalyst and reacting for 1 to 4 hours while maintaining the reactor temperature at 50 to 60 ° C .;
1 to 5 parts by weight of benzophenone or 2-hydroxy-2-methyl-1-phenylpropanone to the reaction product obtained in the UV curing group introduction step. And 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propane {2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl A photopolymerization initiator such as -1-propanone}, followed by a photopolymerization initiator blending step of stirring for 30 to 60 minutes;
Hollow particles surface-modified with 1-20 parts by weight of reactive silane and 80-99 parts by weight of polydiol, 20-60 parts by weight of diisocyanate-terminated polydimethylsiloxane, 60-100 parts by weight of low molecular weight diisocyanate, 5-20 Inorganic hollow surface modified with reactive silane consisting of parts by weight of reactive organic acid, 0.001 to 0.05 parts by weight of condensation catalyst, 5 to 25 parts by weight of difunctional acrylate, 0.1 to 0.5 parts by weight of polymerization inhibitor and 1 to 5 parts by weight of photopolymerization initiator An environmentally friendly urethane bonded link polysiloxane resin reinforced with particles is obtained.
Description
The present invention relates to a method for producing an environment-friendly urethane bond link polysiloxane resin reinforced with surface-modified inorganic hollow particles applicable to paper coatings that do not cause environmental pollution.
As life becomes simpler and the instant culture develops, various paper containers such as disposable paper cups, ramen cups, and paper dishes are emerging. Usually, such coated paper containers (coated), release paper, release paper, graft paper, rust paper, etc. are coated with a polymer material such as polyethylene, and have effects such as waterproofing, oil resistance, and chemical resistance. To improve the strength.
Conventional paper coating method is a method of attaching a polyethylene film on the printing surface for strength and surface gloss, dissolving a resin such as polystyrene in an organic solvent, or hot melt (hot melt) at a high temperature and then surface it It has been applied to and coated.
As an example, in the forming process of the polyethylene film attachment sheet, the polyethylene resin prepared separately on one or both sides of the paper is thermally melted, and then coated on paper with a film coming out of an extruder, and when dried, the polyethylene on the paper The coated paper on which the film layer of resin was formed is completed. Therefore, when the user pours hot water into a container made of polyethylene coated paper or fills the container with other contents, the user not only protects the hot water or the contents in the container, but also enhances the waterproofing and oilproofing effect and the strength of the final product. .
However, such a conventional polyethylene coated paper has the effect of waterproofing and oil proofing, but the working process is not simply simple, especially after use, it is impossible to recycle due to the polyethylene film coating, and finally there is no treatment other than incineration. , There is a problem that the environment is polluted due to dioxin generated during incineration.
The aqueous coating method is difficult to obtain a high gloss product, and this can be solved by increasing the solid content of the water-based coating agent, but there is a big problem that the workability is poor and the uniform surface coating is difficult due to the sharp increase in viscosity and dispersibility. .
U.S. Patent No. 4,287,039 describes a method of dispersing polyester urethane acrylate using a dispersant, but when preparing a paint by such a forced dispersion method, the drying time is the same as the emulsifier used as a surfactant And a large amount of water is present in the coating film depending on the manner, leading to a decrease in physical properties such as water resistance, hardness, gloss.
In addition, U.S. Pat.Nos. 5,135,963, 6,011,078, 6,207,744, 6,335,397, 6,436,540, and 6,538,046, and the like, are known for many UV curable polyurethane aqueous coating dispersions.
However, UV-curable polyurethane aqueous coating dispersions have relatively large molecular weights for dispersion stability in water compared to UV-curable oligomers and UV-curable monomers, which dominate physical properties in conventional oil-based paints. Even if it is increased, it has lower crosslink density after curing than UV-curable oil-based paint, so that physicochemical properties such as adhesion, moisture resistance, hardness, gloss, abrasion resistance, acid resistance, and chemical resistance do not significantly meet the requirements of paper coating. can not do it.
Coating with an organic solvent can obtain a high gloss product, but has the disadvantage of being environmentally harmful and flammable to humans due to organic substances discharged after use.
In addition, volatile organic compounds in the coating agent is an air pollutant that is harmful to the human body that generates ozone (O 3 ) by causing photochemical oxidation with nitrogen oxides by sunlight in the atmosphere.
In particular, benzene formaldehyde and the like is known as a chemical that can cause abdominal pain, headache, dizziness, cancer, leukemia.
Therefore, in recent years, coating agents have increased interest in environmental pollution and stability, and the use of organic solvents is becoming more and more stringent. Therefore, coating agents have been developed in the form of solvent-free or water-dispersible forms.
The development of water-dispersible polyurethane resins, which is being progressed to replace coatings containing volatile organic solvents with environmentally friendly polymers, can be applied to textiles, leather, wood, rubber, adhesives and coatings. The development is largely requested as a binder of a special coating.
In general, a coating material refers to a material that can realize one or more physical properties by coating on various substrates such as plastic, glass, metal, ceramic, wood, and the like. . In the use of most substrates, in the past, it was a stage that satisfies the use of the substrate itself, but now it is a stage that requires multifunctionality and high quality.
In order to solve the above problems, eco-friendly urethane-linked linkage polysiloxane resin reinforced with hollow particles modified with a silane having a reactive group isocyanate (-NCO), amine (amin, -NH 2 ), carboxyl Silanes having reactive groups having-, -COOH) and hydroxy (hydroxyl, -OH) groups, in situ from hollow particles and bifunctional polysiloxanes, low molecular weight diisocyanates, polydiols and reactive organic acids with surface modifications in-situ) polymerized to exhibit performances such as scratch resistance, heat resistance, water resistance, weather resistance, etc., which combine advantages of hardness, gloss, wear resistance, chemical resistance of urethane resin, mechanical properties of urethane resin, water resistance of polysiloxane, heat resistance, etc. Finally, the manufacture of eco-friendly and non-toxic UV curing paper coating resin that does not emit volatile organic compounds or harmful substances to human body It shall be.
Inorganic hollow particles composed of perlite, silica, alumina and titanium dioxide are heat-treated at 100 to 140 ° C to remove moisture or contaminants on the surface. Steps;
Aminosilane such as 20-40 parts by weight of 3-aminopropyl triethoxysilan or 3-isocyanatopropyl triethoxysilane in a reactor equipped with a stirrer and a condensation capacitor Silanes having reactive groups such as carboxysilanes such as isocyanate silane, 3-carboxypropyltriethoxysilane, and 3-hydroxypropyltriethoxysilane, and the like; It is added to an organic solvent such as ~ 80 parts by weight of heptane or toluene and stirred at a speed of 40 ~ 60rpm, while adding 20 ~ 40 parts by weight of heat-treated hollow particles obtained in the hollow particle heat treatment step for 1 to 4 hours After the reaction and filtered to produce a hollow particle surface modified with a reactive silane which is dried for 12 to 48 hours in a vacuum oven at 40 ~ 60 ℃;
80 to 99 parts by weight of the hollow particles surface-modified with 1 to 20 parts by weight of reactive silane prepared in the step of producing the hollow particles surface-modified by the reactive silane in a glass reactor (polyetherdiol or polyester diol) adding a polydiol such as (polyesterdiol) to disperse the surface-modified hollow particles in the polydiol for 1 to 2 hours at 20 to 80 ° C. in an ultrasonic bath;
20 to 60 parts by weight of a polydiol in which 100 parts by weight of surface-modified hollow particles prepared in the step of dispersing the surface-modified hollow particles in a polydiol in a reactor equipped with a thermometer, a stirrer and a condensation capacitor under nitrogen supply Isocyanate-terminated polydimethylsiloxane, 60-100 parts by weight of hexamethylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diisocyanato Low molecular weight diisocyanates such as dicyclohexyl methane (4,4'-diisocyanatodi cyclohexyl methane), tolyene diisocyanate, diphenyl methane diisocyanate, 5 to 20 parts by weight of hydrooxyacetic Hydroxyacetic acid, aminoacetic acid, lysine, N-2-aminoethyl-2-aminoethane sulfonic acid (N-2-aminoethyl-2-a reactive organic acids such as minoethane sulfonic acid), 2,2-bis (hydroxymethyl) propionic acid] and 0.001 to 0.05 parts by weight of 1,4-diazabicyclo Polycondensation catalysts such as (2,2,2) octane [1,4-diazabicyclo (2.2.2) octane], dibutyl tin dilaurate, dibutyl tin maleate The catalyst was added and the reaction temperature was raised to 100-120 ° C. and stirred at 20-50 rpm, followed by in-situ polymerization with the surface modified hollow particles prepared by in-situ polymerization for 6 to 12 hours to form a urethane-linked polysiloxane prepolymer. ) Manufacturing step;
5 to 25 parts by weight of polyethylene glycol diacrylate on the surface-modified hollow particles reacted urethane-linked link polysiloxane prepolymer prepared in the step of preparing the urethane-linked polysiloxane prepolymer reacted with the surface-modified hollow particles ( polymerization inhibitors such as difunctional diacrylates such as polyethylene glycol diacrylate) and 1,3-propanediol dimethacrylate and 0.1 to 0.5 parts by weight of hydroquinone and 0.001 to Introducing an ultraviolet curable group by adding 0.05 parts by weight of a condensation catalyst and reacting for 1 to 4 hours while maintaining the reactor temperature at 50 to 60 ° C .;
1 to 5 parts by weight of benzophenone or 2-hydroxy-2-methyl-1-phenylpropanone to the reaction product obtained in the UV curing group introduction step. And 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propane {2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl A photopolymerization initiator such as -1-propanone}, followed by a photopolymerization initiator blending step of stirring for 30 to 60 minutes;
Hollow particles surface-modified with 1-20 parts by weight of reactive silane and 80-99 parts by weight of polydiol, 20-60 parts by weight of diisocyanate-terminated polydimethylsiloxane, 60-100 parts by weight of low molecular weight diisocyanate, 5-20 Hollow particles surface-modified with reactive silanes composed of parts by weight of reactive organic acid, 0.001 to 0.05 parts by weight of condensation catalyst, 5 to 25 parts by weight of difunctional acrylate, 0.1 to 0.5 parts by weight of polymerization inhibitor, and 1 to 5 parts by weight of photopolymerization initiator. Environmentally-friendly urethane bond link (link) polysiloxane resin production was completed.
As described above, the method for preparing an environment-friendly urethane-linked linkage polysiloxane resin reinforced with inorganic hollow particles surface-modified with the reactive silane of the present invention is completely cured by an ultraviolet curing method so that unreacted compound does not occur, and water resistance It can be used as an industrial coating material such as automobile parts or paper because of its excellent chemical resistance, durability, and mechanical strength. It has the advantage of not releasing volatile organic compounds or harmful components to human body during curing.
BRIEF DESCRIPTION OF THE DRAWINGS Fig.
Figure 2 is an illustration of the reaction equipment of the present invention.
Figure 3 is an electron micrograph of the environmentally friendly urethane link linkage polysiloxane resin fracture surface reinforced with inorganic hollow particles surface-modified with the reactive silane of the present invention.
Looking at the manufacturing method of the environment-friendly urethane bond link polysiloxane resin reinforced with inorganic hollow particles surface-modified with the reactive silane according to the present invention in more detail, the embodiment according to the following.
Inorganic hollow particles composed of perlite, silica, alumina and titanium dioxide are heat-treated at 100 to 140 ° C to remove moisture or contaminants on the surface. Steps;
Aminosilane such as 20-40 parts by weight of 3-aminopropyl triethoxysilan or 3-isocyanatopropyl triethoxysilane in a reactor equipped with a stirrer and a condensation capacitor Silanes having reactive groups such as carboxysilanes such as isocyanate silane, 3-carboxypropyltriethoxysilane, and 3-hydroxypropyltriethoxysilane, and the like; It is added to an organic solvent such as ~ 80 parts by weight of heptane or toluene and stirred at a speed of 40 ~ 60rpm, while adding 20 ~ 40 parts by weight of heat-treated hollow particles obtained in the hollow particle heat treatment step for 1 to 4 hours After the reaction and filtered to produce a hollow particle surface modified with a reactive silane which is dried for 12 to 48 hours in a vacuum oven at 40 ~ 60 ℃;
80 to 99 parts by weight of the hollow particles surface-modified with 1 to 20 parts by weight of reactive silane prepared in the step of producing the hollow particles surface-modified by the reactive silane in a glass reactor (polyetherdiol or polyester diol) adding a polydiol such as (polyesterdiol) to disperse the surface-modified hollow particles in the polydiol for 1 to 2 hours at 20 to 80 ° C. in an ultrasonic bath;
20 to 60 parts by weight of a polydiol in which 100 parts by weight of surface-modified hollow particles prepared in the step of dispersing the surface-modified hollow particles in a polydiol in a reactor equipped with a thermometer, a stirrer and a condensation capacitor under nitrogen supply Isocyanate-terminated polydimethylsiloxane, 60-100 parts by weight of hexamethylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diisocyanato Low molecular weight diisocyanates such as dicyclohexyl methane (4,4'-diisocyanatodi cyclohexyl methane), tolyene diisocyanate, diphenyl methane diisocyanate, 5 to 20 parts by weight of hydrooxyacetic Hydroxyacetic acid, aminoacetic acid, lysine, N-2-aminoethyl-2-aminoethane sulfonic acid (N-2-aminoethyl-2-a reactive organic acids such as minoethane sulfonic acid), 2,2-bis (hydroxymethyl) propionic acid] and 0.001 to 0.05 parts by weight of 1,4-diazabicyclo Polycondensation catalysts such as (2,2,2) octane [1,4-diazabicyclo (2.2.2) octane], dibutyl tin dilaurate, dibutyl tin maleate The catalyst was added and the reaction temperature was raised to 100-120 ° C. and stirred at 20-50 rpm, followed by in-situ polymerization with the surface modified hollow particles prepared by in-situ polymerization for 6 to 12 hours to form a urethane-linked polysiloxane prepolymer. ) Manufacturing step;
5 to 25 parts by weight of polyethylene glycol diacrylate on the surface-modified hollow particles reacted urethane-linked link polysiloxane prepolymer prepared in the step of preparing the urethane-linked polysiloxane prepolymer reacted with the surface-modified hollow particles ( polymerization inhibitors such as difunctional diacrylates such as polyethylene glycol diacrylate) and 1,3-propanediol dimethacrylate and 0.1 to 0.5 parts by weight of hydroquinone and 0.001 to Introducing an ultraviolet curable group by adding 0.05 parts by weight of a condensation catalyst and reacting for 1 to 4 hours while maintaining the reactor temperature at 50 to 60 ° C .;
1 to 5 parts by weight of benzophenone or 2-hydroxy-2-methyl-1-phenylpropanone to the reaction product obtained in the UV curing group introduction step. And 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propane {2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl A photopolymerization initiator such as -1-propanone}, followed by a photopolymerization initiator blending step of stirring for 30 to 60 minutes;
Hollow particles surface-modified with 1-20 parts by weight of reactive silane and 80-99 parts by weight of polydiol, 20-60 parts by weight of diisocyanate-terminated polydimethylsiloxane, 60-100 parts by weight of low molecular weight diisocyanate, 5-20 Hollow particles surface-modified with reactive silanes composed of parts by weight of reactive organic acid, 0.001 to 0.05 parts by weight of condensation catalyst, 5 to 25 parts by weight of difunctional acrylate, 0.1 to 0.5 parts by weight of polymerization inhibitor, and 1 to 5 parts by weight of photopolymerization initiator. Environmentally-friendly urethane bond link (link) polysiloxane resin production was completed.
The inorganic hollow particles are composed of perlite, silica, alumina, titanium dioxide, and the like, and preferably have a particle diameter of 0.01 to 50 μm.
At this time, if the particle diameter of the inorganic hollow particles is less than 0.01㎛, the dispersibility is lowered, and if it is 50㎛ or more, the mechanical strength of the final product is reduced.
[Figure 1] Electron micrograph of inorganic hollow particles
The silane having a reactive group in the surface-modified hollow particle manufacturing step of the reactive silane is 3-aminoethyl triethoxysilan, 3-aminopropyl triethoxysilan, 3- Aminosilane, such as 3-aminopropyl trimethoxysilan, 3-isocyanatopropyl triethoxysilane, or 3-isocyanatopropyltrimethoxysilane (3-isocyanatopropyl isocyanate silanes such as trimethoxysilane), carboxysilanes such as 3-carboxypropyltriethoxy silane and 3-carboxypropyltrimethoxysilane, and 3-hydroxypropyltriethoxysilane ( 20-40 weight part of hydroxysilanes, such as 3-hydroxypropyltriethoxy silane) and 3-hydroxypropyltrimethoxysilane, are used.
In this case, when the content of the silane having the reactive group is less than 20 parts by weight, the surface modification efficiency of the inorganic hollow particles is lowered, and when it is 40 parts by weight or more, economic efficiency is low.
In the preparation of the hollow particles surface-modified with the reactive silane, the organic solvent is aliphatic or benzene such as hexane, heptane, or octane to increase the reaction efficiency as a reaction medium. Although it is preferable to use an aromatic solvent such as benzene, toluene, and xylene, there is no restriction in selecting an organic solvent.
In the step of dispersing the surface-modified hollow particles in polydiol, polydiol is used in an amount of 80 to 99 parts by weight to form a soft segment of a urethane-linked polysiloxane prepolymer. In addition, polyetherdiol such as polytetramethylene glycol, polypropylene glycol, polypropylene polyethylene glycol, polybutylene glycol, or ethylene glycol adipate (ethylene glycol adipate), butanediol adipate (butanediol adipate), butanediol phthalate (butanediol phthalate), hexanediol phthalate (hexanediol phthalate) and polyester diols such as polycaprolactone diol (polycaprolactone diol) and the like can be used.
At this time, when the polydiol content is less than 80 parts by weight, the mechanical strength of the urethane-linked linkage (polysiloxane) formed is lowered, if more than 99 parts by weight, the productivity is lowered due to the viscosity rise during the reaction.
At this time, the molecular weight of the polydiol used is preferably about 500 ~ 6000g / mol, the mechanical strength of the urethane-linked linkage polysiloxane formed when the polydiol molecular weight is less than 500g / mol is lowered and the viscosity rises when the reaction is more than 8000g / mol The productivity decreases accordingly.
The low molecular weight diisocyanate is a hard segment of the urethane-linked linkage polysiloxane prepolymer, which is 2,4-toluene diisocyanate, 2,4-phenylene diisocyanate, 1,6-hexamethylene diisocyanate and iso Poron diisocyanate etc. are preferable and 60-100 weight part is used.
In this case, when the low molecular weight diisocyanate content is less than 60 parts by weight, the mechanical strength of the urethane-linked linkage polysiloxane is lowered, and when it is 100 parts by weight or more, the environmental friendliness is inferior.
remind Diisocyanate-terminated polydimethylsiloxane is used in an amount of 20 to 60 parts by weight in order to impart the water resistance, heat resistance and flexibility of the urethane linkage linkage polysiloxane resin to the urethane linkage linkage polysiloxane prepolymer.
At this time, when the diisocyanate-terminated polydimethylsiloxane content is less than 20 parts by weight, the water-resistance, heat resistance and flexibility of the urethane-linked linkage polysiloxane resin are lowered, and when it is 60 parts by weight or more, the mechanical strength is lowered.
The reactive organic acid is used to impart ionicity in water dispersion, hydrooxyacetic acid, aminoacetic acid, tatarixide, N-2-aminoethyl-2-aminoethane sulfonic acid, 2, 5-20 weight part of 2-bis (hydroxymethyl) propionic acid etc. are used.
In this case, when the reactive organic acid content is less than 5 parts by weight, the water dispersibility of the urethane-linked linkage polysiloxane resin is lowered, and when it is 20 parts by weight or more, the water resistance of the urethane-linked linkage polysiloxane resin is inferior.
The difunctional acrylate may be a polyethylene glycol diacrylate or pentaerythritol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-propanediol diacrylate, as an ultraviolet curing device. 5-25 parts by weight of 3-propanediol diacrylate is used.
At this time, when the bifunctional acrylate content is less than 5 parts by weight, the degree of curing of the urethane-linked linkage polysiloxane resin is lowered, and when it is 25 parts by weight or more, the environmental friendliness is inferior.
The condensation catalyst may be dibutyl tin diacetate or dibutyl tin dilaurate, dibutyl tin malate, dioctyl tin diacetate, 1,4-diazo [2,2,2] -bicyclo- as a reaction catalyst. Octane, etc. can be used, and 0.001 to 0.05 parts by weight is used.
At this time, when the condensation catalyst content is less than 0.001 parts by weight, the viscosity of the urethane linkage linkage (siloxane) formed polysiloxane resin is lowered and the productivity is lowered when it is 0.05 parts by weight or more.
The polymerization inhibitor is used to inhibit the thermal polymerization reaction of the bifunctional acrylate, and hydroquinone or 2-tert-butyl-4-methoxyphenol and butylated dihydroxyan 0.1 to 0.5 parts by weight of butylated hydroxyanisole is used.
At this time, if the content of the polymerization inhibitor is less than 0.1 parts by weight, the thermal polymerization is initiated.
The photopolymerization initiator is a substance that decomposes when irradiated with ultraviolet rays to initiate a curing reaction. It is a benzophenone, 2-hydroxy-2-methyl-1-phenylpropane, and 2-hydroxy-1- [4- (2- It is preferable to use hydroxyethoxy) phenyl] -2-methyl-1-propane etc. individually or in mixture, and 1-5 weight part is added.
At this time, when the content of the photopolymerization initiator is less than 1 part by weight, the photopolymerization rate of the urethane-linked linkage polysiloxane resin is decreased, and when more than 5 parts by weight is added, the economic efficiency of the product is low.
Hereinafter, the present invention will be described in more detail with reference to examples.
However, the scope of the present invention is not limited to the illustrated embodiments.
The ingredients listed in Table 1 were mixed at the respective blending ratios by the following production process.
Example 1
20 g 3-isocyanatopropyltriethoxysilane, 80 g toluene, 40 g Heat-treated at 100 ° C for 12 hours, and added perlite hollow particles to remove moisture or contaminants on the surface, react with stirring at 50 rpm for 2 hours, filter, dry for 12 hours in a vacuum oven at 60 ° C, and 2.5 g in a glass reactor. The surface-modified perlite hollow particles and 97.5 g of polytetramethylene glycol were added and dispersed in an ultrasonic container at 80 ° C. for 1 hour.
Example 2
20 g of 3-aminopropyltriethoxysilane and 80 g of toluene were heated to 100 ° C for 12 hours in a reactor equipped with a stirrer and a condensation condenser. After the reaction with stirring, the mixture was filtered and dried in a vacuum oven at 60 ° C. for 12 hours, and then 2.5 g of surface-modified 40 g Perlite hollow particles and 97.5 g of polytetramethylene glycol are added and dispersed in an ultrasonic container at 80 ° C. for 1 hour.
Example 3
20 g of 3-carboxypropyltriethoxysilane and 80 g of toluene were heated to 100 ° C for 12 hours in a reactor equipped with a stirrer and a condensation condenser. After the reaction was stirred, the mixture was filtered and dried in a vacuum oven at 60 ° C. for 12 hours, and 2.5 g of surface-modified 40 g of perlite hollow particles and 97.5 g of polytetramethylene glycol were added to a glass reactor for 1 hour at 80 ° C. Disperse at
Example 4
50rpm speed for 2 hours by adding 20g of 3-hydroxypropyltriethoxysilane, 80g of toluene and perlite hollow particles to remove surface moisture and contaminants in a reactor equipped with a stirrer and a condenser. After the reaction with stirring with filtration and dried in a vacuum oven at 60 ℃ for 12 hours and then 2.5g of surface-modified 40g in a glass reactor Perlite hollow particles and 97.5 g of polytetramethylene glycol are added and dispersed in an ultrasonic container at 80 ° C. for 1 hour.
Comparative Example
2.5 g of perlite hollow particles and 97.5 g of polytetramethylene glycol were added to the glass reactor and dispersed in an ultrasonic container at 80 ° C. for 1 hour.
[Figure 2] Electron micrographs of perlite hollow particles before (a) and after (b) before treatment with reactive silane
20 g of diisocyanate-terminated and polytetramethylene glycol in which 100 g of surface modified perlite hollow particles (Example 1-4) or perlite hollow particles (Comparative Example) prepared in Examples 1 to 4 and Comparative Example were dispersed Polydimethylsiloxane, 80 g of 1,4-phenylene diisocyanate, 10 g of 2,2-bis (hydroxymethyl) propionic acid and 0.01 g of 1,4-diazabicyclo (2,2,2) Octane was added and the reaction temperature was raised to 120 ° C. and reacted for 40 hours with stirring at 40 rpm. 12 g of 1,3-propanediol diacrylate, 0.1 g of hydroquinone and 0.01 g of 1,4-diazabicyclo ( 2,2,2) Octane was added to a reactor equipped with a thermometer, stirrer, and condensation capacitor under nitrogen supply, and reacted for 2 hours while maintaining the reactor temperature at 60 ° C.
2 g of 2-hydroxy-2-methyl-1-phenylpropanone was added thereto, followed by stirring for 30 minutes to complete production of an eco-friendly urethane link link (link0 polysiloxane resin) reinforced with inorganic hollow particles surface-modified with reactive silane.
[Figure 3] Spectroscopic chart of (a) polyurethane and (b) urethane-linked polysiloxane resin measured by UV spectroscopy
As shown in the spectroscopic chart (b) of the urethane-linked linkage polysiloxane resin measured by the UV spectroscopy of Figure 3,
The evaluation results of Examples (1) to (4) are shown in Table 2 below.
The performance of the eco-friendly urethane-linked linkage polysiloxane resin reinforced with inorganic hollow particles surface-modified with reactive silanes prepared according to the Examples is evaluated according to the following various functional test methods.
(1) Tensile characteristics measurement
Tensile strength and tensile elongation of the specimens were measured three times at a rate of 100 mm / min using QC Tech's Universal Testing Machine (QC-516A2) and the average value was determined. Calculated.
(2) hardness
The hardness of the specimen was measured by Shore D hardness using a hardness tester.
(3) heat resistance
Determination is made using a heat chart measured at 20 ° C./min from room temperature to 800 ° C. using a thermogravimetric analyzer (TGA) under a nitrogen atmosphere.
(4) particle size
The particle size of the water dispersion is measured using a scanning electron microscope or a transmission electron microscope.
(5) conversion rate
After hardening the sample, it is calculated by the content of the non-eluate remaining without leaching when the dissolution test using the leaching solvent.
(6) wear-resistant
It is a transmission device of the motor, and the wear jig for plastic attached to the metal weight of 500 ± 15g is in contact with the sample surface so that the test plate can reciprocate in the long direction. The weight loss rate before and after the abrasion resistance test of the sample was measured.
(7) glossiness
Measure the gloss of the specimen using a gloss meter that generates a 60 ° light source.
At this time, it should be wrapped around the test plate except the part where the light hits from the light source with a black cloth to prevent the light from entering the light source.
Change the measuring point in the test plate and measure 5 times to calculate the average value.
(8) Nonvolatile matter
A strong iron wire of appropriate size to destroy the film formed during evaporation of volatile substances, and about 80mm of inner diameter and flat bottom, and weigh the empty plate with the lid and the weight together. Close it and measure the weight. Calculate the volatile volatility as follows by drying until constant volume in a thermostat maintained at 105 ± 2.
(9) Non-toxicity assessment
Measured using the Energy Dispersive X-ray (EDX) analysis to ensure that the water resistance silicate is in liquid silicates used in the preparation of the inorganic binder it includes toxic heavy metals such as Pb, Cd, Cr 6 + and Hg.
According to the experimental results shown in Table 2, Examples 1 to 4 of the present invention can be seen that the tensile elongation is reduced and wear resistance, heat resistance, in particular tensile strength is improved at least 22% or more than the comparative example.
[Figure 4] (a) Urethane bond link (link0 polysiloxane resin) measured by universal testing machine (b) Comparative example (c) Urethane bond link polysiloxane resin reinforced with inorganic hollow particles surface-modified with non-reactive silane (d Stress-strain curve of Example 1.
Environmentally-friendly urethane-linked linkage polysiloxane resin reinforced with inorganic hollow particles surface-modified with reactive silane according to the present invention possesses excellent physical and chemical properties such as excellent heat resistance and strength as well as wear resistance. It can be widely used as a coating material, the industrial use value is great.
At present, there is little source-based technology for UV-curable paper coatings in Korea. It has another advantage of strengthening national competitiveness and securing a foundation to lead the world market.
The present invention was filed as a research result of "Synthesis of Water Dispersed Urethane Bond Link Polysiloxane and Development of UV Curing Coating Solution", which is a future-leading task of the SME technology development support project implemented by the Small and Medium Business Administration.
Claims (4)
In a reactor equipped with a stirrer and a condenser, 20-40 parts by weight of aminosilane which is 3-aminopropyltriethoxysilane, isocyanate silane which is 3-isocyanatopropyltriethoxysilane, and 3-carboxypropyltriethoxysilane To a silane having a reactive group which is phosphorus carboxysilane, 3-hydroxypropyltriethoxysilane, and hydroxysilane, 60-80 parts by weight of an organic solvent of heptane or toluene was added and stirred at a speed of 40-60 rpm, 20 to 40 parts by weight of the heat-treated inorganic hollow particles obtained in the heat treatment step of the hollow particles are added and reacted for 1 to 4 hours, filtered and surface modified with reactive silane which is dried for 12 to 48 hours in a vacuum oven at 40 ~ 60 ℃ Hollow particle manufacturing step;
80 to 99 parts by weight of polydiol, which is 80 to 99 parts by weight of polyetherdiol or polyesterdiol, was added to the hollow particles surface-modified with 1 to 20 parts by weight of reactive silane prepared in the step of producing the hollow particles surface-modified by the reactive silane to the glass reactor. Dispersing the surface-modified hollow particles dispersed in an ultrasonic container in polydiol at ˜80 for 1 to 2 hours;
In a reactor equipped with a thermometer, a stirrer and a condensation capacitor under nitrogen supply, 100 parts by weight of polydiol in which the surface-modified hollow particles were prepared in the step of dispersing the surface-modified hollow particles in polydiol, and 20 to 60 weight Negative diisocyanate-terminated polydimethylsiloxane, 60 to 100 parts by weight of hexamethylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diisocyanato dicyclohexyl methane, tolyene diisocyanate, Low molecular weight diisocyanate of diphenyl methane diisocyanate, 5-20 parts by weight of hydrooxyacetic acid, aminoacetic acid, lysine, N-2-aminoethyl-2-aminoethane sulfonic acid, 2,2 A reactive organic acid that is bis (hydroxymethyl) propionic acid and 0.001 to 0.05 parts by weight of 1,4-diazabicyclo (2,2,2) octane or dibutyl tin dilaurate, dibutyl tin malate Put a polymerization catalyst and the reaction temperature is raised to 100 ~ 120 ℃ by in situ polymerization with surface-modified hollow particles prepared by in-situ polymerization for 6 to 12 hours while stirring at 20 ~ 50rpm, to prepare a urethane bond link polysiloxane prepolymer Steps;
5 to 25 parts by weight of polyethylene glycol diacrylate in the urethane-linked link polysiloxane prepolymer reacted with the surface-modified hollow particles prepared in the step of preparing the urethane-linked polysiloxane prepolymer reacted with the surface-modified hollow particles B 1,3-propanediol diacrylate, 0.1 to 0.5 parts by weight of hydroquinone series polymerization inhibitor and 0.001 to 0.05 parts by weight of condensation catalyst are added to maintain the reactor temperature at 50 to 60 ℃ 1 UV curable group introduction step of reacting for 4 hours;
1 to 5 parts by weight of benzophenone or 2-hydroxy-2-methyl-1-phenylpropanone and 2-hydroxy-1- [4- (2-hydroxy) to the reaction product obtained in the UV curable group introduction step. Putting a photoinitiator of ethoxy) phenyl] -2-methyl-1-propane and stirring the mixture for 30 to 60 minutes; A method for producing an environmentally friendly urethane bond link polysiloxane resin reinforced with inorganic hollow particles surface-modified with reactive silane, characterized in that it is produced.
The inorganic hollow particles are composed of perlite, silica, alumina and titanium dioxide;
The reactive silane is 3-aminoethyl triethoxysilan, 3-aminopropyl triethoxysilan, 3-aminopropyl trimethoxysilan, or 3-aminopropyl trimethoxysilan. Phosphorus aminosilane, 3-isocyanatopropyl triethoxysilane, or isocyanate silane which is 3-isocyanatopropyl trimethoxysilane, 3-carboxypropyltriethoxy Carboxysilane which is 3-carboxypropyltriethoxy silane or 3-carboxypropyltrimethoxysilane, and 3-hydroxypropyltriethoxy silane or 3-hydroxypropyltrimethoxy Using any one of hydroxysilanes which are silanes (3-hydroxypropyltrimethoxysilane);
The organic solvent is an aliphatic of hexane, heptane, or octane, or an aromatic solvent of benzene, toluene, or xylene. With;
The polydiol is polyethylene glycol, polytetramethylene glycol, polypropylene glycol, polypropylene-polyethylene glycol, polybutylene glycol Polyetherdiol or ethylene glycol adipate, butanediol adipate, butanediol phthalate, hexanediol phthalate and polycaprolactone diol Using polyester diols;
As said diisocyanate, using 2, 4- toluene diisocyanate, 2, 4- phenylene diisocyanate, 1, 6- hexamethylene diisocyanate, and isophorone diisocyanate;
The reactive organic acid may be hydrooxyacetic acid, aminoacetic acid, tartaric acid, N-2-aminoethyl-2-aminoethane sulfonic acid, 2,2-bis (hydroxymethyl) propionic Using an acid;
The difunctional acrylate is polyethylene glycol diacrylate, pentaerythritol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3- Using propanediol diacrylate;
The condensation catalyst is a dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin malate, dioctyl tin diacetate, 1,4-diazo [2,2,2] -bicyclo as a reaction catalyst. Using octane;
The polymerization inhibitor is, using hydroquinone or 2-tert-butyl-4- methoxyphenol and butylated hydroxyanisole;
The photoinitiator is benzophenone, 2-hydroxy-2-methyl-1-phenylpropane and 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1- A method for producing an environmentally friendly urethane bonded link polysiloxane resin reinforced with inorganic hollow particles surface-modified with reactive silane, characterized in that the propane is used alone or in combination.
The hollow particles surface-modified with the reactive silane,
20 to 40 parts by weight of inorganic hollow particles, 20 to 40 parts by weight of silane and 60 to 80 parts by weight of an organic solvent, which is modified by eco-friendly urethane link link reinforced with inorganic hollow particles surface-modified by reactive silane. Polysiloxane resin.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160024470A (en) * | 2014-08-26 | 2016-03-07 | 창성나노텍 주식회사 | Manufacturing method for titanium dioxide coating solution |
| CN108003294A (en) * | 2017-12-07 | 2018-05-08 | 石狮市川大先进高分子材料研究中心 | The cellulose base light-cured resin of quick 3D printing is lifted for Continuous Liquid Phase |
| CN113764122A (en) * | 2021-10-23 | 2021-12-07 | 新亚电子股份有限公司 | Conductive aluminum foil mylar |
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2012
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160024470A (en) * | 2014-08-26 | 2016-03-07 | 창성나노텍 주식회사 | Manufacturing method for titanium dioxide coating solution |
| CN108003294A (en) * | 2017-12-07 | 2018-05-08 | 石狮市川大先进高分子材料研究中心 | The cellulose base light-cured resin of quick 3D printing is lifted for Continuous Liquid Phase |
| CN108003294B (en) * | 2017-12-07 | 2019-11-01 | 石狮市川大先进高分子材料研究中心 | The cellulose base light-cured resin of quick 3D printing is lifted for Continuous Liquid Phase |
| CN113764122A (en) * | 2021-10-23 | 2021-12-07 | 新亚电子股份有限公司 | Conductive aluminum foil mylar |
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