CN115960535B

CN115960535B - LED-UV cured spray-coating color modifier for furniture, and preparation method and application thereof

Info

Publication number: CN115960535B
Application number: CN202211246886.9A
Authority: CN
Inventors: 范新强; 张殿林; 刘伟; 邓文根
Original assignee: Shanghai Junzilan New Material Co ltd
Current assignee: Shanghai Junzilan New Material Co ltd
Priority date: 2022-10-12
Filing date: 2022-10-12
Publication date: 2023-12-12
Anticipated expiration: 2042-10-12
Also published as: CN115960535A

Abstract

The invention relates to the technical field of photo-curing coatings, in particular to the field of IPC C09D175, and more particularly relates to an LED-UV curing spray coating color modifier for furniture, and a preparation method and application thereof. The LED-UV cured spray coating color modifier comprises the following components in parts by weight: 40-60 parts of polyurethane acrylate prepolymer, 30-50 parts of acrylic monomer, 10-20 parts of hydroxyl modified resin, 3-8 parts of adhesion promoter, 5-10 parts of diluent, 3-8 parts of color concentrate, 0.5-3 parts of photoinitiator, 1-3 parts of flatting agent and 1-3 parts of dispersing agent. The weight ratio of the polyurethane acrylate prepolymer to the adhesion promoter is 1: (0.08-0.12), the adhesive force effect is optimal, and the drying rate of the color modifier can be improved when the functionality of the adhesive force promoter acrylic ester phosphate is 8.

Description

LED-UV cured spray-coating color modifier for furniture, and preparation method and application thereof

Technical Field

The invention relates to the technical field of photo-curing coatings, in particular to the field of IPCC09D175, and more particularly relates to an LED-UV curing spray-coating color modifier for furniture, and a preparation method and application thereof.

Background

At present, common color repair methods mainly comprise: the aqueous color correction method is a method of adding aqueous color concentrates into water or alcohol solvents to carry out color correction. The primer is not easy to wet by water, so that the primer is easy to generate flowers, and when an alcohol ether solvent is used, the color is difficult to control because of no film forming substance in the color correction water, so that the flowers are easy to generate. The varnish color-repairing method is difficult to adapt to transparent coloring, and meanwhile, the water-based resin generally contains a large amount of surfactant, so that the latent heat of evaporation of water is large, the drying speed is low, and the construction speed is influenced. The UV color modifier has large monomer occupation and unsatisfactory color moistening and color developing effects on color concentrates, so that the color modification needs to be added with a plurality of solvents, but the solvents are too much and are difficult to volatilize completely, the top paint is sprayed, and the phenomena of whitening, cracking and the like are easy to occur in the later stage after the drying.

CN110862763 discloses a quick-drying aqueous polyurethane color modifier, which mainly comprises self-made aqueous polyurethane resin, and the prepared quick-drying aqueous polyurethane color modifier has the advantages of high drying speed, high construction efficiency, no undercut and no cracking; when diluted by water, the primer has good wettability to the primer and does not generate flowery; the emulsion cannot be broken when the pigment is added, and particles and precipitates are not generated; the method is not only suitable for repairing the water-based bottom coating, but also can be used for repairing the oily coating, but also has a complex preparation process.

CN106519170a discloses a water-based polyurethane resin for wood lacquer color correction and a preparation method thereof. The aqueous polyurethane resin is prepared by using polyethylene glycol modified monoglyceride, the density of double layers among micelles is effectively reduced, and the performances of water resistance, thermal stability of a surfactant and the like of the resin are effectively improved.

Disclosure of Invention

In order to overcome the defects in the invention, the construction efficiency of color repair is improved. The invention provides an LED-UV cured spray-coating color modifier for furniture, a preparation method and application thereof, and the prepared color modifier achieves excellent adhesive force and mechanical property by exploring the proportion of components. Meanwhile, the method is applied to furniture color repair, not only can meet the requirement of batch high-efficiency mechanized production, but also can be used for manually repairing colors and complicated shapes, and the defect of traditional color repair is well filled by radiation curing of a handheld LED-UV light source.

In order to achieve the purpose of the invention, the first aspect of the invention provides an LED-UV cured spray coating color modifier for furniture, which comprises the following components in parts by weight: 40-60 parts of polyurethane acrylate prepolymer, 30-50 parts of acrylic monomer, 10-20 parts of hydroxyl modified resin, 3-8 parts of adhesion promoter, 5-10 parts of diluent, 3-8 parts of color concentrate, 0.5-3 parts of photoinitiator, 1-3 parts of flatting agent and 1-3 parts of dispersing agent.

The polyurethane acrylic ester contains double bonds and urethane bonds in the molecule, so that the polyurethane acrylic ester has good reactivity and excellent optical performance before curing, and has good adhesion and flexibility after curing. The coating obtained by using the aliphatic polyurethane acrylate has good adhesive force and light stability, and the improvement of the functionality can improve the adhesive force, possibly the increase of the density and the polarity of urethane bonds. The viscosity of the system with the too high functionality is increased, the construction difficulty is increased, and further researches show that when the functionality of the aliphatic polyurethane acrylate is 6, not only the excellent adhesion performance is obtained, but also the wettability with the color concentrate can be increased.

The functionality of the polyurethane acrylic ester prepolymer is 4-8.

Preferably, the urethane acrylate prepolymer has a functionality of 5 to 7.

Further preferably, the urethane acrylate prepolymer is an aliphatic urethane acrylate having a functionality of 6, available from Changxing materials industries, inc., model: 6145-100.

The weight ratio of the acrylic monomer to the hydroxyl modified resin is 1: (0.3-0.5) can improve the compatibility of the system, possibly the acrylic monomer reduces the viscosity of the system, while also imparting excellent adhesion properties to the color fixative, possibly due to adequate wetting of the substrate with the appropriate amount of hydroxyl groups.

Preferably, the weight ratio of acrylic monomer to hydroxy modified resin is 1: (0.3-0.5).

Further preferably, the weight ratio of the acrylic monomer to the hydroxy-modified resin is 8:3.

further research shows that when the acrylic monomer selects the difunctional monomer, the difunctional monomer can also be used as a cross-linking agent in the system to provide certain cross-linking density, thereby further improving the mechanical property of the color modifier. The acrylic monomer is tripropylene glycol diacrylate, so that the leveling property of the color modifier can be improved, and excellent processing performance can be obtained, and a plurality of flexible ether bonds in the monomer are possibly present.

Preferably, the acrylic monomer includes at least one of trimethylolpropane triacrylate (CAS: 15625-89-5), tripropylene glycol diacrylate, dipropylene glycol diacrylate (CAS: 57472-68-1).

Further preferably, the acrylic monomer is tripropylene glycol diacrylate (CAS: 42978-66-5), available from Changxing materials industries, inc.

Preferably, the hydroxyl modified resin is purchased from Changshaguangxin new material science and technology Co., ltd., model: LT-408.

The adhesion promoter comprises one or more of zinc oxide, ferric trichloride, molybdenum disulfide, tetraphosphorus pentasulfide, acrylic ester phosphate and silane promoter (purchased from Nanjing XUANWANWAX New Material technology Co., ltd., model: NXH-634).

When the adhesion promoter is acrylic ester phosphate, the adhesion between the material and the surface of the substrate can be improved, the adhesion promoter is particularly suitable for the surface of a metal substrate, and can be a phosphate ferric salt compound generated by the reaction of phosphorus hydroxyl and a metal matrix, and the phosphate ferric salt compound is also one of main components of a phosphate film, so that a structure similar to a rivet is formed on the surface of the metal, a complex is formed with polyvalent metal, and a polymer and the surface of the metal are firmly linked in a covalent bond form, and further research shows that the weight ratio of the polyurethane acrylic ester prepolymer to the adhesion promoter is 1: at (0.08-0.12), the adhesion effect is optimized, and the formed phosphating film has a moderate thickness, and the adhesion between the layers of the excessively thick phosphating film may be reduced, thereby reducing the adhesion.

Preferably, the weight ratio of the urethane acrylate prepolymer to the adhesion promoter is 1: (0.08-0.12).

Further preferred, the weight ratio of urethane acrylate prepolymer to adhesion promoter is 1:0.1.

it was found by accident that the addition of an adhesion promoter improved the dispersibility of the colour concentrate, the weight ratio of adhesion promoter to colour concentrate being 1: (0.8-1.2), in particular, when the adhesion promoter is an acrylate phosphate, the color remains undistorted after the use of the color modifier, possibly because the active groups in the acrylate phosphate increase the wettability of the color concentrate in the system.

The weight ratio of the adhesion promoter to the color concentrate is 1: (0.8-1.2).

The weight ratio of the adhesion promoter to the color concentrate is 1:0.8.

when the functionality of the acrylate phosphate is 8, the drying rate of the color modifier can be improved, and the higher carbon-carbon double bond density possibly improves the photo-curing speed and the crosslinking degree.

Preferably, the adhesion promoter is an acrylate phosphate with a functionality of 8, and is purchased from Qian-you chemical materials Co., ltd., model: UV7424.

The diluent comprises one or more of ethanol, methanol, butanediol, ethyl acetate, butyl acetate, propylene glycol, n-hexane, 4-methyl-2-pentanone and 4-hydroxy-4-methyl-2-pentanone.

Preferably, the diluent comprises one or more of ethanol, butyl acetate and ethyl acetate.

Ethanol, butyl acetate and ethyl acetate with a weight ratio of 1: (0.1-0.3): (0.8-1.2), not only improves the system compatibility, but also improves the leveling property of the film layer and optimizes the drying time, the hydroxyl in the ethanol can improve the compatibility of acrylic ester, a single ethanol solvent can increase the drying time, and the ethyl acetate is added to improve the drying time, so that the volatility of the system can be improved. The butyl acetate can improve film forming performance and leveling performance, and possibly higher volatility can prevent film shrinkage, whitening and disordered flow.

Preferably, the weight ratio of ethanol to butyl acetate to ethyl acetate is 1: (0.1-0.3): (0.8-1.2).

Further preferably, the weight ratio of ethanol, butyl acetate and ethyl acetate is 1:0.2:1.

the photoinitiator comprises: at least one of 1-hydroxy-cyclohexyl-benzophenone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide (TPO), 2-hydroxy-2-methyl-phenylpropanone-1, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylpropanone-1, 2-isopropylthioxanthone, benzoin dimethyl ether, 4- (N, N-dimethylamino), ethyl benzoate, benzophenone, isooctyl N, N-dimethylaminobenzoate, 2,4, 6-trimethylbenzoyl diphenyl phosphorus oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (819) and methyl benzoate.

TPO (2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide) is a deep curing photoinitiator, has good compatibility with a system and higher curing speed, but the volume shrinkage is larger due to rapid curing, and for the system of the invention, the coating is faster to cure, the hardness is higher, but the curing time is possibly reduced due to the fact that the system contains color concentrates. Further studies have found that the addition of a further photoinitiator 819 (phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide) increases the curing time, which is more absorbing in the ultraviolet and visible region and, for pigment-containing coating systems, initiates curing more effectively than other photoinitiators, possibly with greater penetration at 819 wavelengths, which is more accessible to the deep layers of the paint film.

Preferably, the photoinitiators are TPO and 819, both available from Hubei solid wetting technologies Co., ltd.

TPO to 819 weight ratio is 1: (0.3-0.7) can improve deep curing effect, and simultaneously has better surface layer curing effect, and can generate synergistic effect between curing rates of two initiators.

Preferably, the weight ratio of TPO to 819 is 1: (0.3-0.7).

Further preferably, the weight ratio of TPO to 819 is 1:0.5.

preferably, the color concentrate comprises one or more of red (1003), yellow (1002A) and black (1010B), and can be subjected to compound color matching according to different requirements, and the color concentrate is purchased from Shenzhen chemical industry Co., ltd.

The leveling agent comprises: at least one of BYK346, BYK333, BYK301 and EFKA 3777.

Preferably, the leveling agent is EFKA3777, available from Basf (China) Inc.

The dispersant includes at least one of EFKA4310, EFKA4010, EFKA 4560.

Preferably, the dispersant is EFKA4010 available from Basf (China) Inc.

The invention provides a preparation method of an LED-UV cured spray coating color modifier for furniture, which comprises the following steps:

step 1: and adding polyurethane acrylate prepolymer, acrylic monomer, hydroxyl modified resin and dispersing agent, and fully stirring and uniformly mixing to obtain a pre-dispersed mixture.

Step 2: and adding an adhesion promoter, a diluent, a photoinitiator and a leveling agent into the pre-dispersion mixture, and fully and uniformly mixing to obtain the primary color modifier.

Step 3: adding the color concentrates into the primary color modifier, and uniformly mixing to obtain the color modifier.

Preferably, the mixing temperature is 25-45 ℃, the stirring is mechanical stirring, and the stirring speed is 200-400r/min.

Further preferably, the mixing temperature is 40 ℃, the stirring is mechanical stirring, and the stirring speed is 300r/min.

The third aspect of the invention provides an LED-UV cured spray paint color modifier for furniture surface color modification, comprising the following steps:

s1, spraying the prepared color modifier on the surface of furniture;

s2, drying and curing to obtain a color-repairing paint layer;

and S3, spraying UV finish paint on the surface of the color-repairing paint layer, drying and curing to obtain the color-repairing finish paint layer.

Preferably, the spraying in the steps S1 and S3 includes at least one of manual spraying and mechanical spraying.

Preferably, the spraying amount in the step S1 is 25-35g/m ² 。

Further preferably, the spraying amount in the step S1 is 35g/m ² 。

Preferably, the step S2 drying includes one of normal temperature drying and infrared drying; the infrared drying temperature is 40-60 ℃, and the drying time is 4-15min.

Further preferably, the step S2 of drying is infrared drying; the infrared drying temperature is 50 ℃, and the drying time is 5min.

Preferably, the reciprocating paint spraying machine used for spraying is purchased from Dongguan city, mass-Tai automation equipment Co., ltd., model: JD-J1.

Preferably, the curing light sources in the steps S2 and S3 are purchased from 395nm band LED-UV light sources produced by Shenzhen commercial production,

preferably, the curing time in steps S2 and S3 is 2-5min.

Further preferably, the curing time in steps S2 and S3 is 3min.

Preferably, in step S3, the UV topcoat is self-produced by the company, and the model: C2487.

preferably, the spraying amount in the step S3 is 10-20g/m ² 。

Preferably, the step S3 is drying at normal temperature; the drying time is 10min.

Further preferably, the spraying amount in the step S3 is 15g/m ² 。

The beneficial effects are that:

1. the weight ratio of the acrylic monomer to the hydroxyl modified resin is 1: (0.3-0.5), the compatibility of the system can be improved.

2. The weight ratio of the polyurethane acrylate prepolymer to the adhesion promoter is 1: (0.08-0.12), the adhesive force effect is optimal.

3. The weight ratio of the adhesion promoter to the color concentrate is 1: (0.8-1.2), the dispersibility of the color concentrates can be improved.

4. Ethanol, butyl acetate and ethyl acetate with a weight ratio of 1: (0.1-0.3): (0.8-1.2), not only improves the system compatibility, but also improves the leveling property of the film layer and optimizes the drying time.

5. When the functionality of the adhesion promoter acrylate phosphate is 8, the drying rate of the color modifier can be improved.

Detailed Description

Example 1

The LED-UV cured spray coating color modifier for furniture comprises the following components in parts by weight: 60 parts of polyurethane acrylate prepolymer, 40 parts of acrylic monomer, 15 parts of hydroxyl modified resin, 6 parts of adhesion promoter, 8.8 parts of diluent, 4.8 parts of pigment, 1.5 parts of photoinitiator, 2 parts of flatting agent and 2 parts of dispersing agent.

The polyurethane acrylate prepolymer is aliphatic polyurethane acrylate, has a functionality of 6 and is purchased from Changxing materials industry Co., ltd., model: 6145-100.

The acrylic monomer was tripropylene glycol diacrylate (CAS: 42978-66-5), available from Changxing materials industries, inc.

The hydroxyl modified resin is purchased from Changsha Guangxin New Material science and technology Co., ltd., model: LT-408.

The adhesion promoter is acrylic ester phosphate with the functionality of 8, and is purchased from Qian you chemical materials limited company in Zhongshan, model: UV7424.

The color concentrate is yellow (1002A) and is purchased from Shenzhen Yongshengfu chemical Co.

4 parts of ethanol serving as a diluent, 0.8 part of butyl acetate and 4 parts of ethyl acetate.

The photoinitiators were TPO 1 part and 819 0.5 parts, all purchased from Hubei solid wetting technologies Co., ltd.

The leveling agent is EFKA3777, available from Basiff (China).

The dispersant was EFKA4010, available from Basiff (China).

The preparation method of the LED-UV cured spray coating color modifier for furniture comprises the following steps:

The mixing temperature in the steps 1, 2 and 3 is 40 ℃, the stirring is mechanical stirring, and the stirring speed is 300r/min.

An LED-UV cured spray paint color modifier is applied to the surface color modification of furniture, and comprises the following steps:

s1, spraying the prepared color modifier on the surface of furniture;

s2, drying and curing to obtain a color-repairing paint layer;

The spraying in the step S1 is mechanical spraying; the spraying amount is 35g/m ² The method comprises the steps of carrying out a first treatment on the surface of the The spraying uses a reciprocating paint spraying machine, and is purchased from Dongguan city Zhongtai automation equipment limited company, model: JD-J1.

The step S2 is drying to infrared drying; the infrared drying temperature is 50 ℃; the drying time is 5min.

The curing light source in the step S2 is purchased from 395nm wave band LED-UV light source produced by Shenzhen Shuo industry; the curing time was 3min.

The spraying in the step S3 is mechanical spraying; the spraying amount is 15g/m ² The method comprises the steps of carrying out a first treatment on the surface of the The spraying uses a reciprocating paint spraying machine, and is purchased from Dongguan city Zhongtai automation equipment limited company, model: JD-J1.

In the step S3, the UV finish paint is self-produced by the company, and the model is as follows: c2487; the step S3 is drying at 25 ℃; the drying time is 10min.

The curing light source in the step S3 is purchased from 395nm wave band LED-UV light source produced by Shenzhen Shuo industry; the curing time in the step S3 is 1min.

Example 2

The color concentrate is red (1003) and is purchased from Shenzhen chemical industry Co., ltd.

3.8 parts of ethanol serving as a diluent, 1 part of butyl acetate and 4 parts of ethyl acetate.

The photoinitiators were TPO 0.9 parts and 819 0.6 parts, all purchased from Hubei solid wetting technologies Co., ltd.

The leveling agent is EFKA3777, available from Basiff (China).

The dispersant was EFKA4010, available from Basiff (China).

The mixing temperature in the steps 1, 2 and 3 is 38 ℃, the stirring is mechanical stirring, and the stirring speed is 350r/min.

s1, spraying the prepared color modifier on the surface of furniture;

s2, drying and curing to obtain a color-repairing paint layer;

The spraying in the step S1 is mechanical spraying; the spraying amount is 30g/m ² The method comprises the steps of carrying out a first treatment on the surface of the The spraying uses a reciprocating paint spraying machine, and is purchased from Dongguan city Zhongtai automation equipment limited company, model: JD-J1.

The step S2 is drying to infrared drying; the infrared drying temperature is 55 ℃; the drying time is 3min.

The curing light source in the step S2 is purchased from 395nm wave band LED-UV light source produced by Shenzhen Shuo industry; the curing time was 2.5min.

Example 3

The color concentrate is black (1010B) and is purchased from Shenzhen Yongshengfu chemical Co.

The leveling agent is EFKA3777, available from Basiff (China).

The dispersant was EFKA4010, available from Basiff (China).

s1, spraying the prepared color modifier on the surface of furniture;

s2, drying and curing to obtain a color-repairing paint layer;

The spraying in the step S1 is mechanical spraying; the spraying amount is 30g/m ² The method comprises the steps of carrying out a first treatment on the surface of the The spraying is manual spraying.

The step S2 is drying at 25 ℃; the drying time is 12min.

Example 4

The detailed description is the same as example 1; in contrast, in example 4, the color concentrates were: 0.96 parts of black (1010B) 1.92 parts of red (1003) 1.92 parts of yellow (1002A).

Comparative example 1

The detailed description is the same as example 1; in contrast, the adhesion promoter described in comparative example 1 was a silane promoter, available from Nanjuan, new Material technology Co., ltd., model: NXH-634; the UV finishing paint in the step S3 is purchased from Song industry Co., ltd in Jiangmen, model: UV99.

Comparative example 2

The detailed description is the same as example 1; except that the photoinitiator described in comparative example 2 was 1.5 parts of TPO; the TPO was purchased from Hubei solid wetting technology Co., ltd; the UV finishing paint in the step S3 is purchased from Song industry Co., ltd in Jiangmen, model: UV99.

Comparative example 3

The detailed description is the same as example 1; except that 60 parts of the urethane acrylate prepolymer described in comparative example 3, 3.8 parts of an adhesion promoter; the UV finishing paint in the step S3 is purchased from Song industry Co., ltd in Jiangmen, model: UV99.

Performance test method

The color-modifying top coats prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to performance test, and the test data are shown in Table 1.

1) Adhesion test reference standard GB/T9286-1998, test using the hundred method.

2) The pencil hardness test is carried out according to GB/T6739-2006 standard, and the weight is 1000g.

3) Color development effect contrast: the PU color modifier (I department C-3680-3) widely accepted in the market is added with the same color concentrate proportion, the construction is carried out on the same material, the color is compared, and visual feeling is realized by naked eyes, including the spreading and saturation of the color on the material.

Performance test data

TABLE 1

Claims

1. The LED-UV cured spray coating color modifier is characterized by comprising the following components in parts by weight: 40-60 parts of polyurethane acrylate prepolymer, 30-50 parts of acrylic monomer, 10-20 parts of hydroxyl modified resin, 3-8 parts of adhesion promoter, 5-10 parts of diluent, 3-8 parts of color concentrate, 0.5-3 parts of photoinitiator, 1-3 parts of flatting agent and 1-3 parts of dispersing agent;

the adhesion promoter is acrylic ester phosphate, the functionality is 8, and the weight ratio of the polyurethane acrylic ester prepolymer to the adhesion promoter is 1: (0.08-0.12);

the photoinitiator is TPO and 819, and the weight ratio of TPO to 819 is 1: (0.3-0.7).

2. The LED-UV curable spray paint color modifier of claim 1, wherein the adhesion promoter to color concentrate weight ratio is 1: (0.8-1.2).

3. An LED-UV curable spray paint color modifier according to claim 2, wherein the urethane acrylate prepolymer functionality is from 5 to 7.

4. A method of preparing an LED-UV cured spray paint color modifier according to claim 1, comprising the steps of:

step 1: adding polyurethane acrylate prepolymer, acrylic monomer, hydroxyl modified resin and dispersing agent, and fully stirring and uniformly mixing to obtain a pre-dispersed mixture;

step 2: adding an adhesion promoter, a diluent, a photoinitiator and a leveling agent into the pre-dispersion mixture, and fully and uniformly mixing to obtain a primary color modifier;

5. Use of an LED-UV cured spray paint color modifier according to claim 1, for the surface painting of furniture, comprising the steps of:

s1, spraying the prepared color modifier on the surface of furniture;

s2, drying and curing to obtain a color-repairing paint layer;

6. The use of an LED-UV curable spray paint color modifier according to claim 5, wherein the spraying in step S1 comprises at least one of manual spraying and mechanical spraying.

7. The use of an LED-UV curable spray-coating color modifier according to claim 6, wherein the drying in steps S2 and S3 comprises one of normal temperature drying and infrared drying; the drying time of the step S2 or the step S3 is 4-15min.