A kind of printed circuit board cleans uses defoamer
Technical field
The present invention relates to a kind of printed circuit board cleaning defoamer.Because defoamer belongs to fine chemicals, therefore, the invention belongs to technical field of fine chemical preparations.
Technical background
Foam is common phenomena in the live and work.But foam can bring great harm sometimes in industrial production, for example reduce machine operating efficiency, incur loss through delay working time, influence the quality of product etc.The method of eliminating harmful foam mainly contains physical method and chemical method, and the defoamer froth breaking is one of chemical method.Along with the significantly raising of industrial enterprise's production scale and production efficiency, the defoamer froth breaking is more widely used.At present, defoamer has been widely used in the industries such as papermaking, textile printing and dyeing, oil exploitation and refining, coating, emulsion polymerisation, sewage disposal, metal cleaning.
Dry film operation in the printed circuit board production process is to remove unexposed dry film by developer solution.Dry film is the sensitization insulating resin, and developer solution is 0.9~1.5% sodium carbonate liquor.Because dry film constantly dissolves, developer solution produces certain foam in circulatory system spray process, and foam reaches the quality that certain degree will influence development, brings inconvenience to production.Therefore in the industrial processes, often need to add a certain amount of defoamer, to suppress the generation of foam.Defoamer is used in cleaning about printed circuit board, and many patent documentation introductions are arranged, and for example: patent CN 1503057A has invented and has been used for photosensitive anti-etching developer solution froth breaking dispersant, is main froth breaking material with middle-and-high-ranking aliphatic acid (ester) mainly; Patent CN1299694A has invented and has comprised glycerin polyether, alkylamide, presses down bubble reinforcing agent, non-ionic dispersing agent and the composite defoamer that forms of organic solvent; CN1806883A has introduced and has used polyethers to be the used for printed circuit board defoamer of froth breaking material; US5523019 introduces the composition of mineral oil and polyether-polysiloxane copolymers as defoamer, etc., but all can not get desirable disappearing, these several defoamers press down the bubble effect.
The inventor finds by a large amount of experiment, and polyethers defoamer good water solubility is high temperature resistant, strong basicity resisting is strong, but its antifoaming speed and to press down the bubble time all not satisfactory.Be grafted on by condensation and introduce polyether chain on the polysiloxane chain, the polyether-modified polysiloxanes that obtains (being called for short the silicon polyethers) can improve dissolubility, improving froth breaking renders a service, make it not only to have concurrently the advantage of organosilicon and polyethers two defoamers, but also have distinct advantages such as, chemical stability strong, good from milkiness such as contrary dissolubility and heat endurance height.
In polyether segment, the increase of polyoxypropylene segment can improve the hydrophobicity of copolymer, and it is water-soluble and the polyoxyethylene segment increases the meeting raising.If polysiloxanes segment and polyether segment fixed ratio, improve the rare ratio of polyoxy in the polyether chain third, can reduce the solubility of copolymer in water, the reduction cloud point in general, can improve its antifoam performance, but the transparency of system can be affected again.Improve the ratio of polyoxyethylene segment in the polyether chain, hydrophily improves, and can increase its solubility, improves cloud point, can improve its suds suppressing properties, but solubility too conference help the bubble effect.
The inventor finds, by the composite use with silicon polyethers and other polar solvents and anion surfactant, can improve the intermiscibility of silicon polyethers in water, and outward appearance is not subjected to Temperature Influence, owing to be solvent with the deionized water among the present invention, therefore defoamer of the present invention has good security, environmentally safe, and use cost is low.
Summary of the invention
The invention provides a kind of transparence defoamer that can show good antifoaming performance and intermiscibility in printed circuit board cleans, it has safe, stable advantage.
Technical scheme:
A kind of printed circuit board cleans and uses defoamer, it is characterized in that it is made up of following material:
A, froth breaking active matter
Be the silicon polyethers, taken place under the effect of catalyst by hydrogen containing siloxane and the polyethers that contains unsaturated bond that prepared in reaction obtains, specifically the preparation method can consult on technical literature.Its structural formula is as follows:
R in the molecular structure comprises hydrogen atom, methyl, ethyl, propyl group, butyl.Subscript x, y, z, a, b are the degree of polymerization, x is 10~500 integer; Y is 1~50 integer; Z is 3~6 integer; A is 1~40 integer; B is 0~60 integer.The described silicon polyethers preferably dynamic viscosity under 25 ℃ is 60~10,000mPas, and its consumption accounts for 5~15% of defoamer gross mass.
B, organic solvent
Described organic solvent is pure ether solvent, and structural formula is:
H(CH
2)
nO(H(CH
2)
cCHCH
2O)
mH
C be 0 or 1, n be 0~12 integer, m is 1~5 integer.Comprise ethylene glycol, tripropylene glycol butyl ether, DPG butyl ether, propane diols butyl ether, tripropylene glycol methyl ether, dipropylene glycol methyl ether, DPG propyl ether, glycol hexyl ether, diethylene glycol hexyl ether, diethylene glycol butyl ether, butyl glycol ether, 1,4-butanediol monomethyl ether.Consumption of organic solvent accounts for 5~15% of defoamer gross mass.
C, anion surfactant
Described anion surfactant comprises alkylaromatic hydrocarbon class surfactant and alkyl polyoxyethylene ether class surfactant.
Described alkylaromatic hydrocarbon class surfactant structure formula is as follows:
Wherein, R
1Can be carboxylic acid group, sulfate group, sulfonic group and phosphate-based, its position on phenyl ring is not limit; X can be Na
+, K
+, be preferably Na
+R in the structural formula
2Be the alkyl of carbon number 8~20, preferred R
2Alkyl for carbon number 10~16.Subscript p is 0~4 integer.
Described alkyl polyoxyethylene ether class surfactant structure formula is as follows:
R
3(EO)
q R
4X′
Wherein, R
4Can be carboxylic acid group, sulfate group, sulfonic group and phosphate-based; R
3Be the alkyl of carbon number 4~24, preferred R
3Alkyl for carbon number 8~14; X in X ' value and the said structure formula together; Subscript q is 3~30 integer.
Particularly, comprise hexyl benzene sodium sulfonate, hexyl diphenyl ether two sodium sulphate, octyl group benzene sulfonic acid sodium salt, decyl benzene sulfonic acid sodium salt, lauryl sodium sulfate, neopelex, myristyl benzene sulfonic acid sodium salt, cetyl benzene sulfonic acid sodium salt, octyl group diphenyl ether sodium disulfonate, decyl diphenyl ether sodium disulfonate, myristyl diphenyl ether sodium disulfonate, cetyl diphenyl ether sodium disulfonate, detergent alkylate oxygen vinyl sulfonic acid sodium, octyl group polyoxyethylene ether phosphate sodium, dodecyl polyethenoxy ether sodium sulfate, ceteth sodium sulfonate.What the consumption of anion surfactant accounted for invention defoamer total amount is 0~5%.
D, diluent
Be deionized water.Consumption accounts for 65~90% of defoamer gross mass.
Defoamer preparation method among the present invention does not relate to conditions such as heating, freezing, high pressure, as long as each component is mixed, the user in use can add a certain amount of water dilution use.
The specific embodiment
According to the general preparation method of silicon polyethers, synthetic 5 kinds of silicon polyethers as following structural formula:
Table 1 silicon polyethers A1, A2, A3, A4 and A5
The silicon polyethers |
x |
y |
z |
a |
b |
A1 |
27 |
8 |
3 |
14 |
28 |
A2 |
50 |
26 |
3 |
20 |
12 |
A3 |
400 |
20 |
3 |
16 |
55 |
A4 |
150 |
45 |
5 |
33 |
30 |
A5 |
80 |
10 |
3 |
6 |
40 |
Embodiment 1
At room temperature, silicon polyethers A1 is proportionally mixed with diethylene glycol butyl ether, deionized water at 5: 8: 87.
Embodiment 2
At room temperature, with silicon polyethers A2 and glycol hexyl ether, deionized water, neopelex proportionally 8: 13: 78: 1 mixes.
Embodiment 3
At room temperature, with silicon polyethers A3 and butyl glycol ether, deionized water, myristyl diphenyl ether sodium disulfonate, proportionally 6: 10: 81: 3 mixed.
Embodiment 4
At room temperature, will tie silicon polyethers A4 and butyl glycol ether, deionized water, detergent alkylate oxygen vinyl sulfonic acid sodium, proportionally 11: 13: 74: 2 mix.
Embodiment 5
At room temperature, with silicon polyethers A5 and DPG propyl ether, deionized water, hexyl diphenyl ether two sodium sulphate, proportionally 13: 15: 69: 3 mixed.
The performance test of defoamer:
Circuit board cleaning dedicated defoamer sample W and V that the defoamer of embodiment preparation and market is on sale carry out performance comparison.
Specific as follows:
1, antifoaming performance test
Test equipment: 500ml glass cylinder, thermostat, air pump, flowmeter, stopwatch
Test traffic: 250ml/min
Foam liquid preparation: earlier with the aqueous solution of the water-soluble formation 0.1% of unexposed photosensitive resin (wet film), and add the sodium carbonate of foaming liquid measure 1%, make wet film dissolve fully the back with it as foam liquid.
Method of testing: in the 500ml glass cylinder, adding the about 200ml of above-mentioned preparation foam liquid, 30 ℃ of constant temperature.Open air pump and stopwatch, treat that blank foam liquid foam height reaches the 400ml place, to wherein adding defoamer 0.005g, volume of foam V behind the record adding defoamer
MinTime t when reaching this volume
1, continuing then in foam liquid, to add defoamer, the record foam rises to the time t at 400ml place again
2
Table 2 antifoaming performance test comparison
|
Embodiment 1 |
Embodiment 2 |
Embodiment 3 |
Embodiment 4 |
Embodiment 5 |
Sample W |
Sample V |
V
min/ml
|
200 |
200 |
200 |
200 |
200 |
200 |
200 |
t
1/min
|
0.4 |
0.6 |
0.45 |
0.4 |
0.3 |
0.5 |
0.5 |
t
2/min
|
90 |
70 |
100 |
125 |
145 |
85 |
75 |
2, cloud point test
Method of testing: weighing 50ml defoamer solution in the 100ml beaker, heat up, record it by transparent change muddiness, the temperature when lowering the temperature bleach then.
The contrast of table 3 cloud point test
|
Embodiment 1 |
Embodiment 2 |
Embodiment 3 |
Embodiment 4 |
Embodiment 5 |
Sample W |
Sample V |
Cloud point/℃ |
36 |
42 |
50 |
48 |
58 |
39 |
44 |
By above-mentioned test as can be seen, the antifoaming performance of embodiment 5 is best, and the silicon polyethers antifoaming performance that PO content is high will be got well, and is better than existing market selling sample W and V; Improved the heat resistance of system by adding organic solvent and anion surfactant, under normal storage temperature, the system transparency can not change, good stability; And the product self-security that the present invention is composite and safe to use.