KR20040047436A - UV coating materials having Non-slip characteristics - Google Patents

Abstract

PURPOSE: Provided is an UV-curable coating composition, which has excellent anti-slipping property and maintains other physicochemical properties including anti-fouling property, chemical resistance, wear resistance and solvent resistance. CONSTITUTION: The anti-slipping UV-curable coating composition comprises: 30-50 wt% of a photo-polymerizable urethane acrylate oligomer; 20-60 wt% of a functional photo-polymerizable monomer; 2-10 wt% of a photopolymerization initiator; 0.1-3 wt% of a surface tension modifier; and 3-10 wt% of a gloss modifier. The composition further comprises 0.1-5 wt% of a tertiary amine as a co-initiator; 1-5 wt% of a wax as an anti-slipping agent; and 3-20 wt% of a multi-functional monomer of polyglycol having an alkylene oxide number of 7-18.

Description

Non-slip UV Curable Coating Composition {UV coating materials having Non-slip characteristics}

The present invention relates to an anti-slip UV curable coating composition, and more particularly, to a coating composition composed of a photopolymerizable urethane acrylate oligomer, a functional photopolymerizable monomer, a photopolymerization initiator, a surface tension additive, and a gloss adjuster as a tertiary amine. , Additives for anti-slip wax, polyfunctional monomers of polyglycol of 7 to 18 alkylene oxides for forming flexible coating film are added together to produce pollution, chemical and abrasion resistance of existing UV curable coating compositions. The present invention relates to an anti-slip UV curable coating composition that exhibits excellent anti-slip properties while maintaining chemical and physical properties of solvent resistance.

Currently, thermoplastic plastic materials such as vinyl chloride, acrylic, polycarbonate, polyester, and polyamide are widely used in various industrial fields in the form of various film and sheet moldings, and are excellent in light weight, processability, and economic efficiency of thermosetting plastic materials. Due to this, the use of the metal and the glass is replaced by the conventional use. However, these thermoplastic materials have a problem that the surface hardness, scratch resistance, solvent resistance is weak. In order to solve the above problems of physical and chemical properties, attempts have been made for a long time to protect the surface by applying a hard coating on the plastic surface. For example, thermosetting paints such as silicone, acrylic, and melamine resins have been used. However, the thermosetting paints need to be heated for a long time to form a coating film, thereby lowering economic efficiency and possibly damaging the physical properties of the plastic substrate. There was a problem.

Therefore, an attempt has been made to solve the problem of the thermosetting paint generated by the heat applied for a long time, and one of the alternatives is an ultraviolet curable paint.

The UV curable paints are hardened in a short time by irradiation of ultraviolet rays, and thus have high productivity and high surface hardness, and in particular, rapidly replace thermosetting paints in the field of plastic coating. However, the UV curable paint also improved the wear resistance and fouling resistance of the coating film by using a silicone compound, and thus, there is a disadvantage that the surface of the coating film is slippery in a dry state or wet with water, resulting in an accident.

Accordingly, the present inventors have made efforts to improve the slipperiness problem of the UV curable coating composition as described above, the present invention is a photopolymerizable urethane acrylic oligomer, functional photopolymerizable monomer, photopolymerization initiator, surface tension additives and gloss regulator Tertiary amine which acts to promote the photocuring efficiency as an open initiator to the composed coating composition, wax as an anti-slip additive, polyglycol having an alkylene oxide number of 7 to 18 which is effective in preventing slipping by forming a flexible coating film It was completed by adding and manufacturing the polyfunctional monomer of in suitable ratio. Accordingly, the present invention provides an anti-slip UV-curable coating composition that maintains chemical and physical properties of stain resistance, chemical resistance, abrasion resistance, and solvent resistance while showing an excellent effect on anti-slip performance compared to conventional UV-curable coating compositions. have.

The present invention is 30 to 50% by weight of the photopolymerizable urethane acrylate oligomer, 20 to 60% by weight of the functional photopolymerizable monomer, 2 to 10% by weight of the photopolymerization initiator, 0.1 to 3% by weight of the surface tension additive and 3 to 10% by weight of the gloss regulator UV curable coating composition composed of 0.1 to 5% by weight of a tertiary amine, 1 to 5% by weight of an anti-slip additive wax, and 3 to 20% by weight of polyfunctional monomers of polyglycol having 7 to 18 alkylene oxides. It is characterized by the anti-slip UV curable coating composition constituted by adding together.

The present invention will be described in detail as follows.

The present invention relates to a non-slip UV-curable coating composition prepared by adding a releasing agent, an anti-slip additive and a polyfunctional monomer of polyglycol, and includes a photopolymerizable urethane acrylate oligomer, a functional photopolymerizable monomer, a photopolymerization initiator, and a surface tension. It is prepared by adding polyfunctional monomers of tertiary amines, waxes and polyglycols having 7 to 18 alkylene oxides as open reagents to UV curable coating compositions composed of additives and gloss modifiers. The present invention relates to an anti-slip UV curable coating composition which exhibited anti-static properties and retained chemical and physical properties of wear resistance, pollution resistance, chemical resistance, and solvent resistance.

The photopolymerizable urethane acrylate oligomer is generally used in the UV-curable composition 30 to 50% by weight, the urethane acrylate oligomer is an isocyanate, polyol and hydroxy-containing acrylate component prepared by a known method [ Korean Patent Publication No. 1998-075109.

The isocyanate component is used, for example, one or two selected from isophorone diisocyanate, 4,4'-dicyclomethane diisocyanate and hexamethylene isocyanate trimer compound, and the polyol component is, for example, polyester polyol, poly One or two or more selected from ether polyol and caprolactone polyol compounds are used, and the hydroxy-containing acrylate component is, for example, 2-hydroxy (meth) acrylate, 2-hydroxy propyl acrylate and hydroxy One or two or more selected from the caprolactone acrylate compounds are used. The urethane acrylate oligomer prepared by synthesizing the above components is used 30 to 50% by weight, if less than 30% by weight of the coating film properties are lowered, when more than 50% by weight is difficult to adjust the viscosity of the paint.

As another resin, the functional photopolymerizable monomer is used in an amount of 20 to 60 wt%, and the polyalkyl monomer having 3 to 20 wt% of polyglycol having 7 to 18 polyalkylene oxides is used. The polyfunctional monomer of polyglycol having a number of ethylene oxide of 7 to 18 enables flexible coating film formation and shows an effect on slipping.

When the number of the alkylene oxide is less than 7, the acrylate does not exhibit an anti-slip effect, and when it exceeds 18, a problem of deterioration of fouling resistance occurs, and the polyfunctional monomer of polyglycol is, for example, polyethylene glycol diacrylate and polypropylene. 3-20 weight% of 1 type (s) or 2 or more types selected from glycol diacrylate are used. When the use range of the polyfunctional monomer of polyglycol having a number of 7 to 18 of the alkylene oxide is less than 3% by weight, there is no anti-slip effect, and when it exceeds 20% by weight, the anti-slip property is excellent but the fouling resistance of the coating film is lowered. Let's do it.

The functional photopolymerization monomers generally use monofunctional or polyfunctional monomers, and examples of monofunctional monomers include ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxy ethyl acrylate. , 2-hydroxy propyl acrylate, 2-hydroxy butyl acrylate and hydroxy caprolactone acrylate are used in one kind or two or more kinds, and the bifunctional monomer is 1,6-hexanediol diacrylate , Butanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxy Rated Neopentyl Glycol Diacrylate and Proxiated Neo One or two or more of the glycol glycol diacrylates are used, and the trifunctional monomer is selected from trimethylol propane triacrylate, pentaerythritol triacrylate, and glyceryl propoxylated triacrylate. Species or two or more species are used. The photopolymerization monomer may be used in combination according to the required physical properties, and when the amount of the photopolymerizable monomer including the polyfunctional monomer of polyglycol having 7 to 18 alkylene oxide is less than 20% by weight, it is difficult to adjust the viscosity and 60% by weight. If it exceeds, the photocuring speed will become slow and a coating film physical property will fall.

The photopolymerization initiator for the ultraviolet curing reaction of the present invention, for example, selected from benzoin derivatives, α-hydroxy ketone derivatives and benzophenone is used one or two or more, and photocuring by acting as a photocatalyst to the photopolymerization initiator Tertiary amines that promote efficiency and have anti-slip effects such as N, N-dimethylaniline, triethanol amine, 2-dimethylamino ethylmethacrylate and N, N-dimethyl-p-toluidine If 0.1 to 5% by weight of species or two or more is used, less than 0.1% by weight, there is no photocuring efficiency characteristic, and when the content is more than 5% by weight, the cured coating film becomes discolored or the gloss becomes too high. The photopolymerization initiator including the tertiary amine is used in 2 to 10% by weight, when less than 2% by weight, the photocuring efficiency is lowered, and when it exceeds 10% by weight, the physical properties of the coating film are lowered and the curing rate by ultraviolet rays is slowed. Occurs.

In the present invention, the wax added to prevent slippage of the coating composition is, for example, one selected from organic waxes, modified amide waxes, synthetic polymer waxes, polyethylene waxes, polypropylene waxes, polytetrafluoro waxes, and mixtures of polyethylene and amide waxes. Or 1-5 weight% of 2 or more types are used. If the amount of the wax is less than 1% by weight, there is no anti-slip effect. When the amount of the wax is more than 5% by weight, the anti-slip effect is excellent but the pollution resistance is lowered and the touch of the coating is bad.

In addition, the additive for controlling the surface tension of the coating composition is, for example, a silicone compound of 0.1 to one or two or more selected from silicone acrylate and oil (silicone acrylate and oil), B-K-354 and B-K-460 3 weight percent is used. If the amount of the additive is less than 0.1% by weight, fouling resistance is lowered, and when the amount of the additive is more than 3% by weight, the coating film becomes too slippery.

As the gloss adjusting agent of the present invention, the silica powder showing the matting effect of the coating film uses, for example, 3 to 10% by weight of one or two or more selected from fumed silica and micronized silica. If the amount of the glossiness modifier is less than 3% by weight, the matting efficiency is lowered, and when the amount of the glossiness modifier is greater than 10% by weight, fouling resistance becomes low.

In addition to the additives having various functions described above, conventional additives for improving coating properties, improving workability, etc. can be used within the scope of not impairing the present invention.

On the other hand, the present invention is made of a non-slip UV curable coating composition using the above composition consists of the following five steps.

Step 1: The photoinitiator, the functional photopolymerizable monomer, and the open initiator are placed in a 500 ml stainless steel container and warmed to 40 to 45 ° C. to sufficiently dissolve the photoinitiator.

Step 2: The photopolymerizable urethane acrylate oligomer and the dispersant are mixed in the first step and then stirred for 2 to 3 minutes at a speed of 1,000 to 1,500 rpm.

Step 3: After mixing the gloss adjuster and the organic wax in step 2, the mixture is stirred for 20 to 30 minutes at a speed of 2,000 to 2,500 rpm.

Step 4: After mixing the photopolymerizable monomer and the polyfunctional monomer of polyglycol in the above three steps, the mixture is stirred for 5 to 10 minutes at a speed of 1,500 to 2,000 rpm.

Step 5: After mixing the surface tension additive in step 4 and stirred for 10 to 20 minutes at a speed of 1,000 ~ 1,500 rpm.

The UV curable paint composition prepared above shows excellent effects in the field of thermoplastic coating because it has excellent anti-slip, chemical resistance, chemical resistance, abrasion resistance, and solvent resistance.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.

Example 1

Step 1: Photopolymerization initiator 1-hydroxy-cyclohexyl-phenylketone (Ir-184) 2% by weight, benzophenone 3% by weight, functional photopolymerizable monomer 9-ethylene glycol diacrylate (9-EGDA) 15% by weight 3% by weight of open-agent triethanol amine (TEOA) was placed in a 500 ml stainless steel container and warmed to 45 ° C. to sufficiently dissolve the photopolymerization initiator.

Step 2: After mixing 32% by weight of the photopolymerizable urethane acrylate and 1% by weight of the dispersant diluent acrylic oligomer (DOPA-22), the mixture was stirred at a speed of 150 rpm for 3 minutes.

Step 3: After mixing 4% by weight of the fumed silica (fumed silica), 5% by weight of amide wax (C-994) in step 2 and stirred for 30 minutes at a speed of 250 rpm.

Step 4: 10% by weight of the photopolymerizable monomer tetraethylene glycol diacrylate (TTEGDA), 11% by weight of 2-hydroxyethyl acrylate (2-HEA), polyethanol glycol diacrylate (PEGDA, MW: 700) After mixing 13% by weight and stirred for 10 minutes at a speed of 200 rpm.

Step 5: After mixing 1% by weight of the surface tension additive silicone acrylate (silicone acrylate) in step 4 was stirred for 20 minutes at a speed of 1500 rpm to prepare an anti-slip UV curable coating composition.

Physical properties of the prepared paints are shown in Table 1 below.

Example 2

Prepared by the same composition and method as in Example 1,

Step 3: 5 weight% of fumed silica with gloss adjusting agent;

Step 4: An anti-slip UV curable coating composition was prepared using 10 wt% of the functional photopolymerizable monomer 2-HEA instead.

Physical properties of the prepared paints are shown in Table 1 below.

Example 3

Prepared by the same composition and method as in Example 1,

Step 1: 5 wt% of the initiator TEOA;

Step 2: 31 wt% photopolymerizable urethane acrylate;

Step 4: A non-slip UV curable coating composition was prepared using 6% by weight of functional photopolymerizable monomer TTEGDA, 10% by weight of 2-HEA, and 17% by weight of PEGDA.

Physical properties of the prepared paints are shown in Table 1 below.

Example 4

Prepared in the same composition and method as Example 1,

Step 1: 5 wt% of the initiator TEOA;

Step 2: 31 wt% photopolymerizable urethane acrylate;

Step 4: 4.5 wt% functional photopolymerizable monomer TTEGDA, 17 wt% PEGDA;

Step 5: A non-slip UV-curable coating composition was prepared by using 1% by weight of the surface tension additive silicone acrylate and 0.5% by weight of silicone oil.

Physical properties of the prepared paints are shown in Table 1 below.

Example 5

Prepared in the same composition and method as Example 1,

Stage 1: 0.1 wt% TEOA

Step 2: 31 wt% photopolymerizable urethane acrylate;

Step 3: 5 weight% of fumed silica, 2 weight% of amide wax C-994;

Step 4: A non-slip UV curable coating composition was prepared using 7.9% by weight of the photopolymerizable monomer TTEGDA, 13% by weight of 2-HEA, and 19% by weight of PEGDA.

Physical properties of the prepared paints are shown in Table 1 below.

Comparative Example 1

Step 1: Photopolymerization initiator Ir-184 1.5% by weight, benzophenone 3% by weight, photopolymerizable monomer 9-EGDA 18% by weight in a 500 ml stainless steel container and warmed to 45 ℃ to fully dissolve the photoinitiator.

Step 2: After mixing 32% by weight of the photopolymerizable urethane acrylate and 1% by weight of the dispersant DOPA-22, the mixture was stirred at a speed of 1500 rpm for 3 minutes.

Step 3: After mixing 4% by weight of the glodifier fumed silica (fumed silica) and stirred for 30 minutes at a speed of 2500rpm.

Step 4: After mixing 21.5% by weight of the photopolymerizable monomer TTEGDA, 18% by weight of 2-HEA, and stirred for 10 minutes at a speed of 2000 rpm.

Step 5: After mixing 1% by weight of the surface tension additive silicone acrylate (silicone acrylate) was stirred for 20 minutes at a speed of 1500 rpm to prepare an anti-slip UV curable coating composition.

Physical properties of the prepared paints are shown in Table 1 below.

Comparative Example 2

Prepared by the same composition and method as in Comparative Example 1,

1 step: 2 weight% of photoinitiator Ir-184, 15 weight% of photopolymerizable monomer 9-EGDA; Step 2: 31 wt% photopolymerizable urethane acrylate;

Step 3: 5 weight% of fumed silica, 6 weight% of amide wax C-994;

Step 4: A non-slip UV curable coating composition was prepared using 10% by weight of the photopolymerizable monomer TTEGDA, 10% by weight of 2-HEA, and 16% by weight of PEGDA.

Physical properties of the prepared paints are shown in Table 1 below.

Comparative Example 3

Prepared by the same composition and method as in Comparative Example 1,

1 step: 2 weight% of photoinitiator Ir-184, 2 weight% of open initiator TEOA, 15 weight% of photopolymerizable monomer 9-EGDA;

Step 2: 34 wt% photopolymerizable urethane acrylate;

Step 4: A non-slip UV curable coating composition was prepared by using 10% by weight of the functional photopolymerizable monomer TTEGDA, 12% by weight of 2-HEA, and 16% by weight of PEGDA.

Physical properties of the prepared paints are shown in Table 1 below.

Comparative Example 4

Prepared by the same composition and method as in Comparative Example 1,

Step 1: 15 wt% of photopolymerizable monomer 9-EGDA, 3 wt% of open reagent TEOA,

Step 3: 5% by weight of amide wax C-944

Step 4: An anti-slip UV curable coating composition was prepared by using 20.5% by weight of the functional photopolymerizable monomer TTEGDA and 14% by weight of 2-HEA instead.

Physical properties of the prepared paints are shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Pollutant (5 to 1) 4 4 4 4 4 4.5 4 4.2 4 Adhesion 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 Glossiness (60 °) 20 21 31 20 23 15 14 18 15 Sliding) (θ dry 23 23.5 28 22 25 11 15 11.5 16 Wet 39.5 40 39 39.5 42 32 36 27 37

The following shows the test method of Table 1 showing the physical and chemical properties of the coating composition prepared in the Examples and Comparative Examples.

* Curing method: In order to set the curing condition of the UV curing device, the conveyor speed is 2.5 m / min, the distance from the conductor is 25 mm, the lamp coefficient is one lamp, the output voltage is 120 W, and the UV lamp light quantity is 400 It is ~ 600 mj / cm ² and the UV curable paint is applied to the specimen with a coating bar thickness of 15 ㎛ with a doctor bar for forming a 15 ㎛ and then passed through the UV curing device once. Pass the test when it is judged to be fully cured (without traces of nail scratches or insoluble in MEK solvent) after specimen hardening.

* Pollution resistance: After hardening test method, apply circle with a diameter of about 2 cm and then wipe it with dry cloth or cloth before and after drying. It is subdivided into 5 stages based on contamination resistance, and 5 is the best case.

* Adhesiveness: After preparing the specimen by hardening test method, draw 11 parallel lines of equal intervals on the coated specimens and draw 11 parallel lines of equal intervals perpendicular to the parallel lines to make 100 squares (1 mm spacing). Use the tape to press the front face down on the diagonal line and rub with an eraser. Remove at high speed at 45 ^o angle. If all 100 tetrahedrons remain after removing the tape, it is determined that 100/100 adhesion is good.

* Viscosity: Using a Brookfield RVT viscometer, measure the viscosity at 30 rpm using a spindle number 3 while the paint temperature is 30 ° C.

* Slidability (θ): After preparing the specimen by the curability test method, attach the specimen to the glass bottom, put the 500 g weight wrapped on the surface, measure the slippage of the dry state, and wet The slipperiness of the) state is wetted with distilled water and then spread evenly on the specimen with distilled water.

As shown in Table 1, Example 1, in which a polyfunctional monomer of a tertiary amine, wax, and polyglycol having an alkylene oxide number of 7 to 18 as an open reagent was added at an appropriate ratio, compared to Comparative Example 1, which was not added, The anti-slip property was improved to remove paints having improved anti-slip properties of 2 to 2.5 times in the dry state and 1.5 times in the wet state. In addition, Comparative Examples 2, 3, and 4, which reacted by removing the above additives one by one, showed lower glossiness and slipperiness than other examples.

The present invention relates to an ultraviolet curable coating composition composed of a photopolymerizable urethane acrylate oligomer, a functional photopolymerizable monomer, a photopolymerization initiator, a surface tension additive, and a gloss regulator, and has a tertiary amine, a wax, and an alkylene oxide number of 7-18 as an open initiator. Ultraviolet curable coating compositions prepared by adding polyfunctional monomers of polyglycol exhibit very good anti-slip properties, while maintaining chemical and physical properties of wear resistance, stain resistance, chemical resistance, and solvent resistance.

Claims (3)

UV light consisting of 30 to 50% by weight of photopolymerizable urethane acrylate oligomer, 20 to 60% by weight of functional photopolymerizable monomer, 2 to 10% by weight of photopolymerization initiator, 0.1 to 3% by weight of surface tension additive and 3 to 10% by weight of gloss regulator To the curable coating composition, 0.1 to 5% by weight of tertiary amine, 1 to 5% by weight of the anti-slip additive wax, and 3 to 20% by weight of the polyfunctional monomer of polyglycol having 7 to 18 alkylene oxides are added to the curable coating composition. The anti-slip UV curable coating composition, characterized in that the configuration. The tertiary amine of claim 1, wherein the tertiary amine is one or two or more selected from N, N-dimethylaniline, triethanol amine, 2-dimethylamino ethylmethacrylate, and N, N-dimethyl-p-toluidine. An anti-slip UV curable coating composition, characterized in that. The method of claim 1, wherein the wax is one or two or more selected from organic waxes, modified amide waxes, synthetic polymer waxes, polyethylene waxes, polypropylene waxes, polytetrafluoro waxes, and polyethylene wax and amide wax mixtures. An anti-slip UV curable coating composition, characterized in that.