CN101701129A - High-abrasion resistant ultraviolet light solidifying fingerprint resistant coating - Google Patents

High-abrasion resistant ultraviolet light solidifying fingerprint resistant coating Download PDF

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Publication number
CN101701129A
CN101701129A CN200910272845A CN200910272845A CN101701129A CN 101701129 A CN101701129 A CN 101701129A CN 200910272845 A CN200910272845 A CN 200910272845A CN 200910272845 A CN200910272845 A CN 200910272845A CN 101701129 A CN101701129 A CN 101701129A
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coating
acrylate
functionality
percent
nano
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CN200910272845A
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Chinese (zh)
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廖春花
张淑娴
汤兴国
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武汉嘉特利佰联创科技有限公司
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Priority to CN200910272845A priority Critical patent/CN101701129A/en
Publication of CN101701129A publication Critical patent/CN101701129A/en

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Abstract

The invention relates to a light solidifying high-abrasion resistant fingerprint resistant coating which is used for the surfaces of plastic shells of portable electronic products, such as mobile phones, MP3, digital cameras, handheld computers, and the like and comprises the following components: 10-35 percent of high-functionality urethane acrylate, 5-25 percent of bifunctional urethane acrylate, 0.01-20 percent of acrylic ester monomer, 5-20 percent of high-functionality acrylic ester, 5-40 percent of fluorin-contained acrylic ester, 0.01-10 percent of nano inorganic powder filler, 1-5 percent of light initiating agent, 0.01-5 percent of auxiliary agent and 5-30 percent of solvent. The invention improves the fingerprint resistant capability of a coating film by the enrichment and microphase separation of a fluorin-contained group added into the coating on the surface of a coating surface, provides excellent abrasion resistance and hardness by using the polyurethane structure in the coating and the added nano abrasion resistant filler and meets the requirements of abrasion resistance, scratch resistance and fingerprint resistance of the portable electronic products.

Description

High-abrasion resistant ultraviolet light solidifying fingerprint resistant coating

Technical field

The present invention relates to a kind of anti-fingerprint coating of photocuring high abrasion that is used for portable type electronic product plastic casing surfaces such as mobile phone, MP3, digital camera, laptop computer.

Technical background

Ultraviolet-curing paint be a kind of be subjected to UV-irradiation after, the coating of physics and chemical transformation can take place in the short period of time.Compare with traditional seasoning or heat curing coating; ultraviolet-curing paint except have curing speed fast, save the energy, film performance good, to base material applied widely, the volatile solvent consumption is few; also have an outstanding feature: solidification process does not need heating; this for some can not heat-stable plastics, very useful the optics, electronic component, therefore be suitable for very much the protection and the decoration on electronic product plastic casing surfaces such as mobile phone, computer.

Along with social development, the use of portable type electronic products such as mobile phone, MP3, digital camera, laptop computer is more and more frequent, and the human consumer is also more and more higher to the requirement of its outward appearance.Except requiring the attractive in appearance and hand feel and drape of its color, also require its surface abrasion resistance, scratch resistance to hinder to adapt to the needs of carrying.Simultaneously wish that in use product surface has the performance of anti-fingerprintization, just in use product surface is difficult for being stayed after the hand contact vestiges such as water stain, grease, dust, even or also be easy to be removed by wiping after staying spot.

CN1557882A, CN101250340 provide the performance of a kind of ultraviolet-curing paint in order to the anti-fingerprintization of raising plastic casing, but its film performance is difficult to satisfy the high wear-resistant requirement of portable type electronic product.CN1553944A has applied for being used for the anti-fingerprint coating of photocuring and the coating process thereof of coating metal base material, and this coating is not suitable for the ABS or the PC plastic casing of most portable type electronic products.

Summary of the invention

The purpose of this invention is to provide a kind of anti-fingerprint voltinism of rub resistance energy that improves portable type electronic product frostings such as mobile phone, MP3, digital camera, laptop computer, had the photo-cured coating of high-wear resistance simultaneously.

Technical scheme of the present invention is: high-abrasion resistant ultraviolet light solidifying fingerprint resistant coating, comprise: 10～35% high-functionality polyurethane acrylic, 5～25% difunctionality urethane acrylate, 0.01～20% acrylate monomer, 5～20% high functionality acrylate, 5～40% fluorinated acrylate, 0.01～10% nano inorganic powder filler, 1～5% light trigger, 0.01～5% auxiliary agent and 5～30% solvent, above-mentioned per-cent is weight percentage.

High-functionality polyurethane acrylic of the present invention is meant that functionality is 3～9, especially three, six or nine polyurethane acrylate prepolymer, the SM-6318 of Sanmu Group Co., Ltd., Jiangsu (three-functionality-degree) for example, M-80 (six functionality), the M-81 (nine functionality) etc. of Competing company limited.

Two functionality urethane acrylates of the present invention are meant that functionality is two polyurethane acrylate prepolymer, for example get M-60, the M-70 of Competing company limited, the SM-6201 of Sanmu Group Co., Ltd., Jiangsu, SM-6202 etc.

Acrylate monomer of the present invention is: methyl acrylate, ethyl propenoate, vinylformic acid-2-hydroxyl ethyl ester, one or more in butyl acrylate, iso-bornyl acrylate, mono acrylic ester, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, the 2-hydroxyethyl methacrylate.

High functionality acrylate of the present invention is meant the acrylate monomer with 2～6 functionality: 1, the 4-butylene glycol diacrylate, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, the third oxidation neopentylglycol diacrylate, tripropylene glycol diacrylate, PDDA, Viscoat 295, trimethylolpropane trimethacrylate, the third oxidation Viscoat 295, the ethoxyquin Viscoat 295, tetramethylol methane tetraacrylate, in the double pentaerythritol methacrylate one or more.

Fluorinated acrylate of the present invention is: one or more in trifluoromethyl acrylate, methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate, methacrylic acid ten difluoro heptyl esters, vinylformic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate, methacrylic acid ten trifluoro monooctyl esters, vinylformic acid ten trifluoro monooctyl esters, methacrylic acid 17 fluorine monooctyl esters, the vinylformic acid 17 fluorine monooctyl esters.

Nano inorganic powder filler of the present invention is: nano silicon, nano titanium oxide, nano-calcium carbonate, nano zirconium dioxide, nanometer silicon carbide, nano aluminium oxide.

Light trigger of the present invention is: Diisopropyl azodicarboxylate, methyl vinyl ketone, st-yrax, benzophenone, fluorescein, eosin, Benzoin ethyl ether, DEAP, camphorquinone, Alpha-hydroxy isopropyl benzene ketone, Alpha-hydroxy phenylcyclohexane ketone, 2-methyl-4 '-methylthio group-2-morpholinyl Propiophenone, 2,4-diethyl thiazolone etc.

Auxiliary agent of the present invention comprises one or more of following composition: flow agent, defoamer, wetting agent, pigment.

Solvent of the present invention comprises one or more of following composition: vinyl acetic monomer, N-BUTYL ACETATE, propyl carbinol, dimethylbenzene, toluene, acetone, 4-methyl 2 pentanone, Virahol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol ether, ethylene glycol ether acetate, propylene-glycol ethyl ether acetic ester.

The preparation method of coating of the present invention only need proportionally stir each component of coating and get final product, and can mix with random order.

High-abrasion resistant ultraviolet light solidifying fingerprint resistant coating provided by the invention can be used as the ultraviolet-curing paint of portable type electronic product plastic casing, utilize the fluoro-containing group that adds in this coating to improve the anti-fingerprint ability of filming in the enrichment and the microphase-separated of film coated surface, utilize the polyurethane structural in the coating and the nano wearproof filler of interpolation that excellent abrasive energy and hardness are provided simultaneously, satisfy that portable type electronic product is wear-resisting, scratch resistance is hindered and the requirement of anti-fingerprintization.

The photo-cured coating of the anti-fingerprint of high abrasion provided by the invention has the following advantages:

1. employed high-functionality polyurethane acrylic double bond content is big, bridge formation density height, can form filming of high rigidity, high abrasion; Excellent water tolerance and levelling property are arranged; Adherence to plastics such as ABS and PC is good.

2. add two functionality urethane acrylates and improve the toughness of high-functionality polyurethane, reducing films explosion occurs when " high low-temperature test "; And two the functionality urethane acrylate because double bond content is few, and bridge formation density is low, can effectively reduce " reaction shrink "; The content of " polyurethane structural " of resin is big, can strengthen wear resistance.

3. adding nanometer inorganic filler, nanometer inorganic filler to the enhancing of filming, significantly improves the abrasion property energy under the prerequisite that does not influence the film coated surface glossiness.

4. the high chemical stability that utilizes the low surface energy of fluorinated acrylate, high bond energy and show can improve the ageing-resistant performance of coating.Because the polar difference, fluoro-containing group tends to surface enrichment in film process, even thereby under the less fluorinated acrylate consumption, coatingsurface fluorine content is still higher, greatly reduces the surface energy of filming.The enrichment meeting of fluoro-containing group simultaneously makes the surface form trickle coarse outstanding structure, reduces the contact area of external dirt and film coated surface, and external dirt is difficult for adhering to and easily wiping, has improved its anti-fingerprint performance.

In sum, above-mentioned coating is used for portable type electronic product plastic outer layers such as mobile phone, MP3, digital camera, laptop computer, has improved wear resistance and has given anti-fingerprint voltinism energy.And preparation is simple, only need each component is mixed in proportion, but automatic production, the production efficiency height is easy to scale operation.

Embodiment

Embodiment 1:

With following component: the high-functionality polyurethane acrylic M-80 of six functionality of Competing company limited () 20%; Difunctionality urethane acrylate (getting the M-60 of Competing company limited) 15%; Acrylate monomer (methyl acrylate) 10%; High functionality acrylate (Viscoat 295) 15%; Fluorinated acrylate (vinylformic acid 17 fluorine monooctyl esters) 15%; Nano inorganic powder filler 5% (silicon-dioxide of particle diameter 10～50nm); Light trigger (benzophenone) 2%; Auxiliary agent (flow agent BYK-3060.5%, defoamer BYK-0660.2%, wetting agent BYK-1640.3%) 1%; Solvent (5% vinyl acetic monomer, 5% N-BUTYL ACETATE, 7% 4-methyl 2 pentanone) 17%.Join in the stirring tank, mix, form coating.Above per-cent is weight ratio.

Above paint spay-coating to the ABS base material, is tested film performance behind the ultraviolet light polymerization.Described UV curing method and film performance testing method are known technology in the coating property field tests, do not repeat them here.

Film performance:

1. outward appearance is not had foaming, peels off, and does not have obvious variable color;

2. contact angle is 120 °, has excellent anti-fingerprint;

3. pencil hardness 3H (GB/T6739-96);

4. sticking power 100/100 (GB/T9286-88);

5. wear resistance: RCA abrasion are 1300 times;

6. acid resistance: 5% sulfuric acid soaks 48h does not have considerable change; Alkali resistance: 5%NaOH soaks 48h does not have considerable change: 5%NaCl soaks 48h does not have considerable change.

Embodiment 2:

With following component: the high-functionality polyurethane acrylic M-81 of nine functionality of Competing company limited () 15%; Difunctionality urethane acrylate (getting the M-70 of Competing company limited) 25%; Acrylate monomer (butyl acrylate) 8%; High functionality acrylate (trimethylolpropane trimethacrylate) 5%; Fluorinated acrylate (vinylformic acid 17 fluorine monooctyl esters) 25%; Nano inorganic powder filler (titanium dioxide of particle diameter 20～60nm) 5%; Light trigger (DEAP) 2%; Auxiliary agent (flow agent BYK UV35000.5%, defoamer BYK-0660.2%, wetting agent BYK-1610.3%) 1%; Solvent (3% ethylene glycol monomethyl ether, 5% acetone, 6% 4-methyl 2 pentanone) 14%.Join in the stirring tank, mix, form coating.Above per-cent is weight ratio.

Above paint spay-coating to the ABS base material, is tested film performance behind the ultraviolet light polymerization.

Film performance:

1. outward appearance is not had foaming, peels off, and does not have obvious variable color;

2. contact angle is 140 °, has excellent anti-fingerprint;

3. pencil hardness 2H (GB/T6739-96);

4. sticking power 100/100 (GB/T9286-88);

5. wear resistance: RCA wears away 1400 times (the wear-resisting tester of Norman RCA, load 175g);

6. acid resistance: 5% sulfuric acid soaks 48h does not have considerable change; Alkali resistance: 5%NaOH soaks 48h does not have considerable change: 5%NaCl soaks 48h does not have considerable change.

Embodiment 3:

With following component: high-functionality polyurethane acrylic (SM-6318 of Sanmu Group Co., Ltd., Jiangsu) 25%; Difunctionality urethane acrylate (SM-6201 of Sanmu Group Co., Ltd., Jiangsu) 15%; Acrylate monomer (iso-bornyl acrylate) 5%; High functionality acrylate (tetramethylol methane tetraacrylate) 8%; Fluorinated acrylate (methacrylic acid ten trifluoro monooctyl esters) 20%; Nano inorganic powder filler (particle diameter is 20～30 nano-calcium carbonate) 8%; Light trigger (Alpha-hydroxy phenylcyclohexane ketone) 5%; Auxiliary agent (flow agent BYK 3580.8%, defoamer BYK-0660.2%, wetting agent EFKA-48000.3%, Holliday ultramarine HG 0.5%) 1.8%; Solvent (4% propylene-glycol ethyl ether acetic ester, 5% dimethylbenzene, 3.2% butanols) 12.2%.Join in the stirring tank, mix, form coating.Above per-cent is weight ratio.

Above paint spay-coating to the ABS base material, is tested film performance behind the ultraviolet light polymerization.

Film performance:

1. outward appearance is not had foaming, peels off, and does not have obvious variable color;

2. contact angle is 140 °, has excellent anti-fingerprint;

3. pencil hardness 2H (GB/T6739-96);

4. sticking power 100/100 (GB/T9286-88);

5. wear resistance: RCA wears away 1500 times (the wear-resisting tester of Norman RCA, load 175g);

6. acid resistance: 5% sulfuric acid soaks 48h does not have considerable change; Alkali resistance: 5%NaOH soaks 48h does not have considerable change; Perspiration resistance: 5%NaCl soaks 48h does not have considerable change.

Embodiment 4:

With following component: the high-functionality polyurethane acrylic M-81 of nine functionality of Competing company limited () 20%; Difunctionality urethane acrylate (SM-6202 of Sanmu Group Co., Ltd., Jiangsu) 10%; Acrylate monomer (10% methyl acrylate, 5% butyl acrylate) 15%; High functionality acrylate (ethoxyquin Viscoat 295) 15%; Fluorinated acrylate (methacrylic acid ten difluoro heptyl esters) 20%; Nano inorganic powder filler 5% (particle diameter is the zirconium dioxide of 40～50nm); Light trigger (Alpha-hydroxy isopropyl benzene ketone) 2%; Auxiliary agent (flow agent BYK 3580.8%, defoamer BYK-066 0.2%, wetting agent EFKA-48000.3%, Holliday ultramarine HG 0.5%) 1.8%; Solvent (3% vinyl acetic monomer, 5% N-BUTYL ACETATE, 3.2% ethylene glycol ether acetate) 11.2%.Join in the stirring tank, mix, form coating.Above per-cent is weight ratio.

Above paint spay-coating to the ABS base material, is tested film performance behind the ultraviolet light polymerization.

Film performance:

1. outward appearance is not had foaming, peels off, and does not have obvious variable color;

2. contact angle is 130 °, has excellent anti-fingerprint;

3. pencil hardness 3H (GB/T6739-96);

4. sticking power 100/100 (GB/T9286-88);

5. wear resistance: RCA wears away 1200 times (the wear-resisting tester of Norman RCA, load 175g);

6. acid resistance: 5% sulfuric acid soaks 48h does not have considerable change; Alkali resistance: 5%NaOH soaks 48h does not have considerable change: 5%NaCl soaks 48h does not have considerable change.

Embodiment 5:

With following component: the high-functionality polyurethane acrylic M-80 of six functionality of Competing company limited () 10%; Difunctionality urethane acrylate (SM-6202 of Sanmu Group Co., Ltd., Jiangsu) 18%; Acrylate monomer (butyl methacrylate) 1%; High functionality acrylate (double pentaerythritol methacrylate) 8%; Fluorinated acrylate (10% methacrylic acid hexafluoro butyl ester, 20% vinylformic acid 17 fluorine monooctyl esters) 35%; Nano inorganic powder filler (particle diameter is the aluminum oxide of 10～30nm) 9%; Light trigger (2-methyl-4 '-methylthio group-2-morpholinyl Propiophenone) 3%; Auxiliary agent (flow agent BYK 37770.8%, defoamer BYK 0550.2%) 1%; Solvent (8% ethylene glycol ether acetate, 5% dimethylbenzene, 2% 4-methyl 2 pentanone) 15%.Join in the stirring tank, mix, form coating.Above per-cent is weight ratio.

Above paint spay-coating to the PC base material, is tested film performance behind the ultraviolet light polymerization.

Film performance:

1. outward appearance is not had foaming, peels off, and does not have obvious variable color;

2. contact angle is 140 °, has excellent anti-fingerprint;

3. pencil hardness 2H (GB/T6739-96);

4. sticking power 100/100 (GB/T9286-88);

5. wear resistance: RCA wears away 1300 times (the wear-resisting tester of Norman RCA, load 175g);

6. acid resistance: 5% sulfuric acid soaks 48h does not have considerable change; Alkali resistance: 5%NaOH soaks 48h does not have considerable change: 5%NaCl soaks 48h does not have considerable change.

Claims (10)

1. high-abrasion resistant ultraviolet light solidifying fingerprint resistant coating, comprise: 10～35% high-functionality polyurethane acrylic, 5～25% difunctionality urethane acrylate, 0.01～20% acrylate monomer, 5～20% high functionality acrylate, 5～40% fluorinated acrylate, 0.01～10% nano inorganic powder filler, 1～5% light trigger, 0.01～5% auxiliary agent and 5～30% solvent, above-mentioned per-cent is weight percentage.
2. coating according to claim 1 is characterized in that: the functionality of described high-functionality polyurethane acrylic is 3～9.
3. coating according to claim 1 and 2, it is characterized in that: described acrylate monomer is methyl acrylate, ethyl propenoate, vinylformic acid-2-hydroxyl ethyl ester, one or more in butyl acrylate, iso-bornyl acrylate, mono acrylic ester, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate or the 2-hydroxyethyl methacrylate.
4. coating according to claim 1 and 2 is characterized in that: described high functionality acrylate is meant the acrylate monomer with 2～6 functionality.
5. coating according to claim 4, it is characterized in that: described high functionality acrylate is 1, the 4-butylene glycol diacrylate, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, the third oxidation neopentylglycol diacrylate, tripropylene glycol diacrylate, PDDA, Viscoat 295, trimethylolpropane trimethacrylate, the third oxidation Viscoat 295, the ethoxyquin Viscoat 295, in tetramethylol methane tetraacrylate or the double pentaerythritol methacrylate one or more.
6. coating according to claim 1 and 2 is characterized in that: described fluorinated acrylate is one or more in trifluoromethyl acrylate, methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate, methacrylic acid ten difluoro heptyl esters, vinylformic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate, methacrylic acid ten trifluoro monooctyl esters, vinylformic acid ten trifluoro monooctyl esters, methacrylic acid 17 fluorine monooctyl esters or the vinylformic acid 17 fluorine monooctyl esters.
7. coating according to claim 1 and 2 is characterized in that: described nano inorganic powder filler is nano silicon, nano titanium oxide, nano-calcium carbonate, nano zirconium dioxide, nanometer silicon carbide or nano aluminium oxide.
8. coating according to claim 1 and 2, it is characterized in that: described light trigger is Diisopropyl azodicarboxylate, methyl vinyl ketone, st-yrax, benzophenone, fluorescein, eosin, Benzoin ethyl ether, DEAP, camphorquinone, Alpha-hydroxy isopropyl benzene ketone, Alpha-hydroxy phenylcyclohexane ketone, 2-methyl-4 '-methylthio group-2-morpholinyl Propiophenone or 2,4-diethyl thiazolone.
9. coating according to claim 1 and 2 is characterized in that: described auxiliary agent comprises one or more in flow agent, defoamer, wetting agent, the pigment.
10. coating according to claim 1 and 2 is characterized in that: described solvent comprises in vinyl acetic monomer, N-BUTYL ACETATE, propyl carbinol, dimethylbenzene, toluene, acetone, 4-methyl 2 pentanone, Virahol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol ether, ethylene glycol ether acetate, the propylene-glycol ethyl ether acetic ester one or more.
CN200910272845A 2009-11-24 2009-11-24 High-abrasion resistant ultraviolet light solidifying fingerprint resistant coating CN101701129A (en)

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