Background technology
Wood lacquer is to use in a kind of protection, the decorative coating in places such as timber, plank, density board, furniture, kitchen cabinet, desk, paper panel, and in China, the production of wood lacquer, usage quantity are only second to industrial paint, and annual consumption is above 400,000 tons.
Several stages has been experienced in the development of wood lacquer, the earliest be the raw lacquer (cry again state lacquer, lacquer) of single component, be to be main raw material(s) with natural tung oil, oleum lini.Along with the development of chemical industry, the appearance of high molecular polymer, alkyd paints had appearred in the wood lacquer industry afterwards, was that prepared alkyd paint, the enamel paint with single component is main products during beginning.To the sixties, China introduces technology, and has successfully developed solvent-type double-component urethane formaldehyde alkyd woodenware lacquer.This be solidifying agent with the urethane resin, be the solvent-type double-component wood lacquer of the basic resin of lacquer with the short-oil alkyd, strong adhesion, good hand touch, hardness height have very high, excellent decoration effect, have satisfied the demand of people's GOOD TASTE life.Yet this solvent-type double-component urethane formaldehyde alkyd woodenware lacquer is a thinner with the organic solvent, influences environment.Simultaneously, because the curable urethane resin agent is starting material with tolylene diisocyanate (TDI), wherein can residual free TDI, and the TDI that is discharged into air belongs to noxious chemical, has a strong impact on, threatens the healthy of people.At present,, reduce consumption of organic solvent, because the difficulty of technical elements is difficult to thoroughly eliminate the free TDI in the polyurethane curing agent though industry requires to reduce free TDI content again and again.So coating industry has turned to environmental protection, healthy water-borne coatings field at the seventies with the wood lacquer research direction.
Aqueous woodware paint in China research relatively early, but up to 80 years, kind appearance few in number is arranged, single component wherein arranged, two-pack is also arranged.Aqueous woodware paint has three big technical bottlenecks to influence the popularization and the use of aqueous woodware paint: the one, and hardness is low; The 2nd, rate of drying is slow; The 3rd, fullness ratio can not satisfy people's requirement.Self-crosslinking single component has used appropriate self-crosslinking technology, and the hardness of paint film, fullness ratio increase than volatile dry type single component, but index, requirement that hardness, fullness ratio still do not reach bicomponent system.Two-pack is to carry out crosslinking reaction with reactable group-OH (hydroxyl) on reactable group-NCO on the polyurethane curing agent molecular structure and component B (the coating with lacquer basic resin) molecular structure, so the hardness of aqueous wood lacquer with double components, fullness ratio can both be met the need of market.Yet owing to all having taked with water to be solvent, thinner, the organic cosolvent of the organic pure ethers of high boiling point that adds in lacquer causes drying varniss speed slower in addition, particularly in the winter of cold, has had a strong impact on the normal construction of wood lacquer especially.At present, the hardness aspect is best with the dual-component aqueous polyurethane wood lacquer, is solidifying agent with the waterborne polyurethane resin that contains crosslinkable groups-NCO promptly, serves as the basic resin of lacquer with water-based hydroxy acryl acid resin or water-based hydroxyl group containing polyester resin.The curing of paint film is carried out crosslinking reaction by NCO with activity hydroxy and is realized.Yet, because technicals, at present second component (coating with lacquer basic resin) but on the molecular structure reactive hydroxyl groups (OH) be secondary hydroxyl, influenced curing cross-linked, the rate of drying of aqueous woodware paint.
Summary of the invention
Technical problem to be solved by this invention is the slow deficiency of rate of drying that overcomes the prior art aqueous woodware paint, and a kind of new bi-component acrylic aqueous woodware paint is provided.
For solving above technical problem, the present invention takes following technical scheme:
A kind of bi-component acrylic aqueous woodware paint comprises the first component and the second component of independent packaging, and wherein, the first component is a polyurethane curing agent, and the second component is the basic resin of lacquer, and in weight part, the composition of raw materials of second component is as follows: alcohol 5%~60%; Vinylformic acid 0.1%~5%; Butyl acrylate 5%~20%; Methyl methacrylate 2%~20%; Acrylic ester contains primary hydroxy monomers 10%~30%; By the preparation of solution continuous polymerization, it is formula (I) or the compound of formula (II) expression or the mixture of the two that described acrylic ester contains primary hydroxy monomers by above-mentioned raw materials for initiator 0.01%~2%, second component.
Among the present invention, each feed composition generally obtains from commercial source, wherein acrylic ester contain primary hydroxy monomers can also be by well-known route of synthesis of chemical field and method preparation.
Concrete aspect according to the present invention, the acrylic ester of formula (I), formula (II) expression contains primary hydroxy monomers and can synthesize by esterification.Concrete route of synthesis and technology are: select for use vinylformic acid, tetramethylolmethane at nitrogen or CO 2 gas-shieldedly carry out esterification in 160 ℃~220 ℃ down, utilize refluxing xylene to take the water that esterification generates out of.Its Chinese style (I) vinylformic acid, tetramethylolmethane equivalence ratio are 1: 4, and its Chinese style (II) vinylformic acid, tetramethylolmethane equivalence ratio are 1: 2.
Preferably, as the purity of the alcohol of second component raw material more than or equal to 99%.
Preferred feedstock prescription according to second component of the present invention is: alcohol 50%~60%, vinylformic acid 1%~5%, butyl acrylate 10%~15%, methyl methacrylate 12%~18%, acrylic ester contain primary hydroxy monomers 10%~20% and initiator 0.5%~1%.
Above-mentioned initiator can be persulphates such as Potassium Persulphate or ammonium persulphate, Sodium Persulfate.
According to a concrete aspect of the present invention, the preparation process of second component is as follows:
1. initiator evenly is divided into four parts, evenly obtains the spirituous solution of four parts of initiators with ten times alcohol Potassium Persulphate dissolving;
2. vinylformic acid, butyl acrylate, methyl methacrylate and acrylic ester are contained primary hydroxy monomers and drop into header tank, drop into the spirituous solution of the initiator that 1. a step obtain simultaneously, mix, dissolve evenly standby;
3. the alcohol with remainder drops into reactor, adds the 1. spirituous solution of gained initiator of a step simultaneously, leads to steam, opens stirring, to refluxing and keeping refluxing, begin to drip 2. gained mixture of step, control rate of addition, make step 2. the gained mixture in 3.5-4 hour, drip off.Dripping off the back continues to keep refluxing 0.8~1.2 hour, add a step 1. the spirituous solution of gained initiator continue to keep refluxed 0.8~1.2 hour, add the 1. spirituous solution of gained initiator of last a step again, continue to keep refluxing 1.5~2.5 hours, inspection by sampling is qualified with transformation efficiency 〉=99.8%, promptly stops steam after qualified, logical water quench filters and packages to room temperature.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
The present invention has used to have highly active acrylic ester and contains primary hydroxy monomers as the basic resin reaction group of lacquer, has improved the curing speed of paint film; Use alcohol to replace the solvent of deionized water, be beneficial to the raising rate of drying, and do not use high boiling pure ethers organic cosolvent in the present invention's prescription, reduced organic solvent volatilization pollution on the environment as aqueous woodware paint.
Embodiment
The present invention is further detailed explanation below in conjunction with specific embodiment, but the invention is not restricted to these embodiment.
Embodiment 1
Present embodiment provides a kind of bi-component acrylic aqueous woodware paint, comprises the first component and the second component of independent packaging, and wherein the first component is polyurethane curing agent (solid content is 100%), and the composition of raw materials and the preparation process of second component are as follows:
(1), composition of raw materials (in weight part): 0.80 part of 15.00 parts of the compounds of 50.20 parts of alcohol (purity 〉=99%), 1.5 parts in vinylformic acid, 17.5 parts of butyl acrylates, 15.00 parts of methyl methacrylates, formula (I) expression and initiator (Potassium Persulphate).Acrylic ester contains primary hydroxy monomers,
Wherein, the compound of formula (I) expression prepares as follows:
72.06 kilograms of Acrylic Acid Monomers, 136.15 kilograms of tetramethylolmethanes, backflow dimethylbenzene are dropped into esterifying kettle for 5 kilograms, feed nitrogen.Heat up, be stirred to 160 ℃ and begin to react water outlet, be warmed up to 220 ℃ naturally, keeps 220 ℃ ± 5 ℃, continue esterification 4 hours, the survey acid value that begins to take a sample is when acid value≤2 are qualified.Can lower the temperature and pack behind the cool to room temperature.
(2), preparation process: obtain the second component according to above-mentioned raw materials prescription and following steps:
1. Potassium Persulphate evenly is divided into four parts, evenly with ten times alcohol Potassium Persulphate dissolvings;
2. vinylformic acid, butyl acrylate, methyl methacrylate and acrylic ester are contained primary hydroxy monomers and drop into header tank, drop into the Potassium Persulphate spirituous solution that 1. a step obtains simultaneously, mix, dissolve evenly standby;
3. the alcohol with remainder drops into reactor, adds the Potassium Persulphate spirituous solution that 1. a step obtains simultaneously, leads to steam, opens stirring, to refluxing and keeping refluxing, begin to drip the mixture that 2. step obtains, the control rate of addition, the mixture that 2. step is obtained dripped off in 3.5-4 hour.Make in 3.5~4 hours and drip off, dripping off the back continues to keep refluxing one hour, add the Potassium Persulphate spirituous solution that 1. a step obtain and continue to keep refluxing one hour, add the Potassium Persulphate spirituous solution that 1. last a step obtains again, continue to keep refluxing two hours, get final product inspection by sampling, with transformation efficiency 〉=99.8% is qualified, can stop steam after qualified, and logical water quench is to room temperature, filter and package second component solid content 50 ± 2%.
According to the bi-component acrylic aqueous woodware paint of present embodiment in use, join lacquer at 1: 1 according to first, second component solid content weight ratio, concrete proportioning and other material carry out according to the general requirement of aqueous woodware paint.
Embodiment 2
Present embodiment provides a kind of bi-component acrylic aqueous woodware paint, and it comprises the first component and the second component of independent packaging, and wherein the first component is a polyurethane curing agent, and the composition of raw materials and the preparation process of second component are as follows:
(1), composition of raw materials: (in weight part): 0.70 part of 12.00 parts of the compounds of 50.80 parts of alcohol (purity 〉=99%), 2.5 parts in vinylformic acid, 20.00 parts of butyl acrylates, 14.00 parts of methyl methacrylates, formula (I) expression and initiator (Potassium Persulphate).
(2), preparation process: with embodiment 1, gained second component solid content 50 ± 2%.
According to the bi-component acrylic aqueous woodware paint of present embodiment in use, join lacquer at 0.8: 1 according to first, second component solid content weight ratio, concrete proportioning and other material carry out according to the general requirement of aqueous woodware paint.
Embodiment 3
Present embodiment provides a kind of bi-component acrylic aqueous woodware paint, and it comprises the first component and the second component of independent packaging, and wherein the first component is polyurethane curing agent (solid content 100%), and the composition of raw materials and the preparation process of second component are as follows:
(1), composition of raw materials: (in weight part): 1 part of 16.5 parts of the compounds of 40 parts of alcohol (purity 〉=99%), 2.5 parts in vinylformic acid, 20 parts of butyl acrylates, 20 parts of methyl methacrylates, formula (II) expression and initiator (Potassium Persulphate).
Wherein, the compound of formula (II) expression prepares as follows:
144.16 kilograms of Acrylic Acid Monomers, 136.15 kilograms of tetramethylolmethanes, backflow dimethylbenzene are dropped into esterifying kettle for 6 kilograms, feed nitrogen.Heat up, be stirred to 160 ℃ and begin to react water outlet, be warmed up to 220 ℃ naturally, keeps 220 ℃ ± 5 ℃, continue esterification 4 hours, the survey acid value that begins to take a sample is when acid value≤2 are qualified.Can lower the temperature and pack behind the cool to room temperature.
(2), preparation process: with embodiment 1, gained second component solid content 60 ± 2%.
According to the bi-component acrylic aqueous woodware paint of present embodiment in use, join lacquer at 0.5: 1 according to first, second component solid content weight ratio, concrete proportioning and other material carry out according to the general requirement of aqueous woodware paint.
Embodiment 4
Present embodiment provides a kind of bi-component acrylic aqueous woodware paint, and it comprises the first component and the second component of independent packaging, and wherein the first component is polyurethane curing agent (solid content 100%), and the composition of raw materials and the preparation process of second component are as follows:
(1), composition of raw materials: (in weight part): 1.2 parts of 26.8 parts of the compounds of 30 parts of alcohol (purity 〉=99%), 4 parts in vinylformic acid, 20 parts of butyl acrylates, 18 parts of methyl methacrylates, formula (II) expression and initiators (Potassium Persulphate).
(2), preparation process: with embodiment 1, gained second component solid content 70 ± 2%.
According to the bi-component acrylic aqueous woodware paint of present embodiment in use, join lacquer at 1: 1 according to first, second component solid content weight ratio, concrete proportioning and other material carry out according to the general requirement of aqueous woodware paint.
The performance index that the wood lacquer of embodiment 1 to 4 is joined behind the lacquer are tested, see Table 1.
Table 1
As seen from Table 1, aqueous woodware paint rate of drying according to the present invention is fast, and hardness and fullness ratio also all can be met the need of market.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.