CN1114334A - Coating resin composition - Google Patents
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- CN1114334A CN1114334A CN 95105561 CN95105561A CN1114334A CN 1114334 A CN1114334 A CN 1114334A CN 95105561 CN95105561 CN 95105561 CN 95105561 A CN95105561 A CN 95105561A CN 1114334 A CN1114334 A CN 1114334A
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Abstract
A coating resin compound contains at least a silicone compound (A) of the structural formula (1), (2), (3) and (4), a hydroxyl-containing resin (B) and a cross-linking agent (C) having a functional group reactive with a hydroxyl. The functional group which is at least partly contained in the silicone compound and containing hydroxyl resin exists as salts.
Description
The present invention relates to a kind of resin combination, especially a kind of coating resin composition.
For example being used to protect, the film of skin must have good weather resistance and good weatherproof ability.Coating resin as making this film is known that the resin combination that contains a large amount of silicone resins.For example, the coating resin of a kind of vinylformic acid that comprises the organopolysiloxane resin that is mixed with alcoholic hydroxyl or vibrin has been disclosed in JP-A-2-64181 (term " JP-A " is used for this paper and means " unexamined open Japanese patent application ").
Except weather resistance and weatherproof ability, above-mentioned film also must have the antifouling property as its outward appearance effect of maintenance.Usually owing to thinking that the antifouling property of film and the tackiness and the electrostatic property of this film are closely related, so be conceived to the contamination resistance that these key elements attempt to improve film.For example, proposed a kind of design, therefore the tackiness of film avoids sticking on the described film from physically having suppressed pollutent owing to the raising of its hardness reduces in this design.The another kind design that proposes comprises the preparation that hydrophilic nmature is arranged that adds in the coating such as the basic metal sulfonium salt, to form a kind of film of antistatic property decline, has suppressed pollutent static thus and has sticked on the film.
Yet with regard to tackiness or antistatic property, the improvement of film antifouling property aspect generally speaking regular meeting causes that film characteristics comprises that weatherproof ability, tackiness and snappiness descend.For example improve film hardness and cause the snappiness of this film to descend, and when by hydrophilic preparation the antistatic property of film being reduced, because the adding hydrophilizing agent causes this film weatherproof ability and tackiness to degenerate in described coating.Therefore the antipollution character of improvement film is difficult when will keep the general property of film needs.
Although the surface irregularity that has proposed to pass through to regulate this film is to improve the antifouling property of film, it is not too remarkable that this technology only is effective in the contamination that makes this film, therefore, can not become a kind of means of improving antifouling property in essence.
The objective of the invention is to improve the antifouling property of film, keep the necessary performance of common film to comprise the weatherproof ability simultaneously.
Coating resin composition of the present invention comprises the resin (B) of silicone compounds (A), hydroxyl, and have can with the linking agent (C) of the functional group of hydroxyl reaction.Silicone compounds is a kind of compound that is selected from the silicone compounds of average group compound general formula (1), (2), (3) and (4) expression at least.Be contained at least a silicone compounds and the hydroxy-containing resin is that form with salt exists to small part functional group.
In above-mentioned general formula, A is a kind of organic residue at least, and it is selected from by following chemical formula (ⅰ), (ⅱ) with (ⅲ) in organic residue of expression, and described chemical formula is:
B is-CH
2CH
2CH
2OCH
2CH
2OH,
X is 3-acryl propoxy-or 3-methacryloyl propoxy-,
Y is the monovalence substituting group, it contain at least be selected from-COOH ,-SO
3H and-NR
2 2(R wherein
2Be organic residue) in a kind of group.
R
1Be aryl, aralkyl, or have 1～6 carbon atom alkyl and
A, b, c and d respectively are following number of repeat unit.
1≤a≤20
0.5≤b≤3
1≤c≤10
0＜d≤6
In this coating resin composition, partly or entirely silicone compounds can with part hydroxy-containing resin bonding to form silicone modified resin.
The hydroxyl value that the resin of hydroxyl has is from 20 to 300 (good especially is from 40 to 120) for example.
The ratio of mixture ((A): (B)) of silicone compounds (A) and hydroxylated resin (B) is for example 3: 97-70: 30 (good especially is 5: 95-40: 60).
Silicone compounds (A)
Be used for silicone compounds of the present invention and can use average group compound general formula (1), (2), (3) and (4) expression.In the present invention, these silicone compounds or use separately or two or more use together.
In these silicone compounds, A is the organic residue in a kind of organic residue that is selected from following general formula (ⅰ), (ⅱ) and (ⅲ) represents at least.
B is a group of pressing chemical formulation,
—CH
2CH
2CH
2OCH
2CH
2OH
X is 3-acryl propoxy-or 3-methacryloyl propoxy-.Y be univalent contain at least a kind of being selected from-COOH ,-SO
3H and-NR
2 2The substituting group of middle group.This group of representing with Y can be straight chain also can be side chain.R
2Preferably hydrogenous organic residue.This organic residue has no particular limits, and the example comprises alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl and the tertiary butyl.Two or more X and two or more Y can be contained in the silicone compounds and (that is to say that two or more different groups of being represented by X may all exist with two or more different groups of being represented by Y).
In above-mentioned silicone compounds, R
1Be aryl (for example phenyl or naphthyl), aralkyl (for example nonyl phenyl) or alkyl (for example methyl, ethyl, propyl group, butyl or hexyl) with 1-6 carbon atoms.Consider R from industrial point
1Methyl or phenyl preferably.The R of two or more
1Can be present in simultaneously in the silicone compounds and (that is to say that two or more are different uses R
1The group of expression may exist).
In showing average group compound general formula (1)-(4) of silicone compounds, a, b, c and d respectively are following repeating unit numerical value.
1≤a≤20
0.5≤b≤3
1≤c≤10
0＜d≤6
Preferably a, b, c and d respectively are following numerical value.
2≤a≤15
0.7≤b≤1.5
2≤c≤7
0.5＜d≤3
If a is less than 1, the weatherproof ability of film then can not be improved by silicone compounds.If a surpasses 20, silicone compounds then can reduction and the reactivity and the consistency of α, β-ethylenically unsaturated monomers.If b is less than 0.5, the copolymerization ratio regular meeting of silicone compounds and α, β-ethylenically unsaturated monomers reduces, and this point can cause the increase of residual unreacted silicon ketone compound content and the performance of infringement copolymer resin, if b surpass 3 or d surpass 6, in the polymerization process of silicone compounds and α, β-ethylenically unsaturated monomers pectisation can appear, so that can not show gratifying film forming properties.If c less than 1, then is difficult to make film of the present invention to have enough wetting abilities.If c surpasses 10, then the viscosity of described compound increases, and can descend with the reactivity and the consistency of α, β-ethylenically unsaturated monomers.
In each silicone compounds by above-mentioned average group compound general formula (1), (2), (3) and (4) expression, the arrangement of repeating unit can be by blocked, random formula or another kind of mode and carry out.
Being used for silicone compounds of the present invention (A) can be by following acquisition.(I) silicone compounds of representing by average group compound general formula (1)
This silicone compounds can obtain from the market.For example, silicone compounds " KR-9206 " (being made by Japanese shin-Etsu Chemical Industry company limited) can be used as the silicone compounds by average group compound general formula (1) expression.(II) silicone compounds of representing by average group compound general formula (2)
This silicone compounds can be reacted with maleic anhydride or itaconic anhydride by the silicone compounds of average group compound general formula (1) expression and synthesize.Specifically, the silicone compounds of average group compound general formula (1) expression contact with maleic anhydride, the end group OH group of B passes through the silicone compounds that obtains to have the A that above-mentioned general formula (ⅰ) represents with the esterification of maleic anhydride in the silicone compounds thus.When the silicone compounds of average group compound general formula (1) expression contacts with itaconic anhydride, can esterification take place and the silicone compounds of obtain to have general formula (ⅱ) and the A that (ⅲ) represents equally.(III) silicone compounds of representing by average group compound general formula (3)
The example of this silicone compounds comprises the compound that following structural is represented.In the given structural formula of this paper, each represent methylidene of Me and Ph and phenyl.
This silicone compounds can be synthetic by following approach.At first, the silicone compounds that synthesizes average group compound general formula (5) expression.
In above-mentioned general formula (5),
X is 3-acryl propoxy-or 3-methacryloyl propoxy-,
Z be at least one be selected from 3-Racemic glycidol propoxy-(3-glycidoxypropyl), (2-(3 ', 4 '-epoxycyclohexyl) ethyl, 3-hydroxypropyl, 3-(2 '-hydroxy ethoxy) propyl group and 3-(4 '-(3 ', 3 '-methylol) butoxy) group in the propyl group
R
1Be aryl, aralkyl or alkyl with 1～6 carbon atom and
A, b and c respectively are following number of repeat unit.
1≤a≤20
0.5≤b≤3
1≤c≤10
Can carry out the reaction of silicon oxide alkanisation by phenyl methyl hydrogen polysiloxanes and the alkene with organo-functional group to this silicone compounds synthesizes.This phenyl methyl hydrogen polysiloxanes can synthesize, as with following reaction (A).
Use the phenyl methyl hydrogen polysiloxanes, can synthesize desired silicone compounds, for example by following reaction (B).
At the silicone compounds example as average group compound general formula (3) expression, under synthetic above-named compound (a) and (b) and the situation (c), following silicone compounds (a ') and (b ') can synthesize as stated above.
Use acid anhydrides, these silicone compounds (a ') of amine compound or sulfoacid compound modification and (b ') can obtain desired silicone compounds (a) and (b) and (c), and specifically, these reactions are as described below.
(IV) silicone compounds of representing by average group compound general formula (4)
The example of described silicone compounds comprises following compounds.
This silicone compounds can be synthetic by following approach.
At first, synthesize the silicone compounds of representing by average group compound general formula (6).In formula (6), X, Z, R
1, a has and the identical implication of average group compound general formula (5) with b.
This silicone compounds can synthesize; for example; by tetramethyl disiloxane and 3-methacryloyl propoxy-methyl-dimethoxysiloxane and water; the reaction product of reacting in the presence of the acid catalyst and being obtained is being arranged and by octamethylcyclotetrasiloxane and octaphenyl cyclotetrasiloxane and soda balance and the reaction product that is obtained is carried out balanced reaction and synthetic by making described two kinds of reaction product and trifluoromethayl sulfonic acid.This route of synthesis is as described in following (C).
As the example of the silicone compounds of representing by average group compound general formula (4), under the synthetic above-mentioned compound of enumerating (e), (f) and situation (g), can synthesize following silicone compounds (e ') and (f ') as stated above.
Can obtain desired silicone compounds (e), (f) and (g) with acid anhydrides, amine compound or these compounds of sulfoacid compound modification (e ') and (f ').Specifically these reactions are as described below.
As the above-mentioned appointed compound (11) of the silicone compounds example of average group compound general formula (4) expression, can synthesize by in the synthetic method of synthetic silicone compounds (c) by average group compound general formula (6) expression, adding following allylic cpd in the compound (II) of above-mentioned regulation.
CH
2＝CH(CH
2)
8COOH
The above-mentioned the present invention's of being used for silicone compounds has from 200 to 100,000 number-average molecular weight, and preferably from 500 to 20,000.If its number-average molecular weight is lower than at 200 o'clock, then be difficult to form film with sufficient mechanical strength.From another point of view, the number-average molecular weight above 100000 can cause thus with the resin of hydroxyl and the consistency of linking agent and weaken, make to be difficult to obtain abundant solidified film.Number-average molecular weight of the present invention is measured with gel permeation chromatography (GPC).The resin of hydroxyl (B)
Be used for hydroxy-containing resin of the present invention and be not particularly limited, all types of resins all can use, as long as they contain hydroxyl.The example of representational hydroxy-containing resin comprises acrylic resin, Synolac, vibrin, Resins, epoxy, aminoplast(ic) resin, the Synolac of acryl modification, acryl modified polyester resin and polycarbonate resin.
Be used for hydroxy-containing resin of the present invention good especially be to have hydroxyl value 20 to 300, preferred 30 to 100 hydroxy-containing resin.If when using hydroxyl value to be lower than 20 hydroxy-containing resin, the reaction of this resin and linking agent is inadequate, and cause mechanical and physical performance to reduce.If use hydroxyl value to be higher than 300 hydroxy-containing resin, the consistency variation of described resin and linking agent is so that can not obtain enough solidified films.Linking agent (c)
Use in the present invention linking agent be for can be at silicone compounds intermolecular, form crosslinked between the intermolecular or silicone compounds of hydroxy-containing resin and hydroxy-containing resin.
In the present invention, having in its molecule of any compound can be with the functional group of hydroxyl reaction, all can use and without particular limitation as linking agent, and the example of linking agent comprises polyisocyanate compounds, melamine-formaldehyde resin and dibasic acid anhydride.When using this linking agent, be contained in wherein functional group be contained in the reaction and become the three-dimensional cross-linked silicone compounds and the resin of hydroxyl at room temperature or under the temperature that improves of hydroxyl in silicone compounds and the hydroxy-containing resin, produce thus and have the film that physical strength is improved.
Using possess hydrophilic property segmental linking agent, is effective obtaining aspect the further improved film of antifouling property.The example of possess hydrophilic property segmental linking agent comprises that poly ethyldiol modified isocyanic ester " N2-753 " is (by Japanese Dai-Nippon InK ﹠amp; Chem-icals company makes).Resin combination
Coating resin composition of the present invention comprises silicone compounds, hydroxy-containing resin and above-mentioned linking agent.The part or all of functional group that above-mentioned silicone compounds and hydroxy-containing resin had should exist with the form of salt.That is to say that the part or all of acidic functionality or the basic functionality that are contained in silicone compounds and the hydroxy-containing resin should exist with the form of salt.A kind of representative salify technology is to use in acid or the alkali and silicone compounds and hydroxy-containing resin.Under the situation of hydroxy-containing resin, the formation of salt structure can be in its synthetic process, and for example use has the comonomer of salt structure such as Sodium styrene sulfonate and carries out.
In resin combination of the present invention, silicone compounds (A) is adjusted to 3: 97-70 with the ratio of mixture ((A): (B)) of hydroxylated resin (B): 30, be preferably 5: 95-40: 60.If the ratio of silicone compounds is lower than at 3 o'clock, then the performance of silicone compounds can not show fully, and the result for example can cause this film weatherproof ability to degenerate.From another point of view, if the ratio of silicone compounds surpasses at 70 o'clock, then the consistency between silicone compounds and hydroxy-containing resin degenerates, and causes film hardness decline and antifouling property also to descend.
The amount that linking agent adds must be suitable for improving crosslinking reaction.Although this add-on is restriction especially not, usually by counting 10-30% based on the weight of silicone compounds and hydroxy-containing resin mixture.
In resin combination of the present invention, partly or entirely silicone compounds can form silicone modified resin with part hydroxy-containing resin bonding.This composition is preferred, because it makes film have higher weatherproof ability.Be suitable for the not restriction especially of method of silicone compounds and hydroxy-containing resin bonding.The example is included in and adds the method for silicone compounds with the resin of usefulness silicone compounds modification hydroxyl in the process of synthesizing hydroxy-containing resin.Effective means comprises adding urethane resin, melamine-formaldehyde resin, dibasic acid anhydride or other analogue in addition, so that the resin-bonded of silicone compounds and hydroxyl.The utilization of coating resin composition
Coating resin composition of the present invention with can be used as coating after tinting pigment for example, pigment extender, necessary solvent and general additive mix.This coating can be used as for example coating of buildings outer wall.
The film that forms by the coating that contains resin combination of the present invention, owing to small part silicone compounds and hydroxy-containing resin, forming the salt structure, so have the water-wetted surface of appropriateness.The degree of described hydrophilic nmature is represented by water contact angle, is generally 65 ° or low.Be easy to water and remove owing to stick to pollutent on the film, therefore described film has good antifouling property.In addition, described film also has the advantageous property of general film, comprises weatherproof ability, weather resistance and snappiness, because in this resinous principle silicone compounds is arranged.
With reference to listed example the present invention at length is described below, but is not construed as limiting the invention.
Hereinafter, all " umber " all by weight.Production example 1 (synthesizing of silicone compounds)
By 40 parts of silicone compounds by following average group compound general formula (7) expression, 44 parts xylol, 4 parts maleic anhydride and the mixture of 0.5 part of dibutyl tin oxide were reacted 1 hour down at 100 ℃.(worker R) surveys this reaction by means of infrared absorption spectrum, proves conclusively finishing of this reaction by this spectrum.
Thus, obtained to press the solution of the silicone compounds of column average composition general formula (8) expression.This silicone compounds is equivalent to the silicone compounds of above-mentioned average group compound general formula (2) expression.
Production example 2 (synthesizing of silicone modified acrylic resin soln)
In 3 hours the timed interval, in the reaction mixture of the xylol of the 40 parts of silicone compounds solution that contains that production example 1 obtained and 70 parts, under keeping 110 ℃, drip a kind of solution that contains 10 parts of methacrylic acids, 20 parts of 2-hydroxyethyl meth acrylates, 25 parts of 2-ethylhexyl methacrylic esters, 25 parts of uncle-butyl methyl acrylate and 2 parts of uncle-butyl peroxy-2-ethylhexoates.After 1 hour, in 30 minutes,, make resulting mixture ageing 2 hours then at this mixture ageing toward wherein dripping 0.5 part of uncle-butyl peroxy-2-ethylhexoate and 30 parts of xylol.As a result, obtain silicone modified acrylic resin soln.Be contained in the acrylic resin modified resin made by silicone compounds and hydroxy-containing resin bonding of being equivalent to of silicone in this solution.In this silicone modified acrylic resin, the hydroxyl value of acrylic resin part is 86.Production example 3 (synthesizing of silicone modified acrylic resin soln)
Contain 20 parts by in the silicone compounds of following average group compound general formula (9) expression and 70 parts of xylol and the reaction mixture of insulation under 110 ℃ toward a kind of, in 3 hours time, drip a kind of 10 parts of methacrylic acids that contain, the solution of 20 parts of 2-hydroxyethyl meth acrylates, 25 parts of 2-ethylhexyl methacrylic esters, 25 parts of uncle-butyl methyl acrylate and 2 parts of uncle-butyl peroxy-2-ethylhexoates.After 1 hour, in 30 minutes,, make resulting mixture ageing 2 hours again at this mixture ageing toward wherein dripping 0.5 part of uncle-butyl peroxy-2-ethylhexoate and 30 parts of xylol.As a result, obtain the solution of silicone modified acrylic resin.The acrylic resin modified resin that is equivalent to silicone compounds and the formation of hydroxy-containing resin bonding of the silicone that in this solution, contains.In this silicone modified acrylic resin, the hydroxyl value of acrylic resin part is 86.
Production example 4 (synthesizing of silicone modified acrylic resin soln)
Contain silicone compounds and 70 parts of xylol of 20 parts of following average group compound general formulas (10) expressions and remain in the reaction mixture under 110 ℃ toward a kind of, in 3 hours, drip a kind of solution that contains 10 parts of methacrylic acids, 20 parts of 2-hydroxyethyl meth acrylates, 25 parts of 2-ethylhexyl methacrylic esters, 25 parts of uncle-butyl methyl acrylate and 2 parts of uncle-butyl peroxy-2-ethylhexoates.After 1 hour, in 30 minutes,, make resulting mixture ageing 2 hours then at this mixture ageing to wherein dripping 0.5 part uncle-butyl peroxy-2-ethylhexoate and 30 minutes xylol.As a result, obtained silicone modified acrylic resin soln.Be contained in the acrylic resin modified resin that is equivalent to silicone compounds and the formation of hydroxy-containing resin bonding of silicone in this solution.In this silicone modified acroleic acid resin, the hydroxyl value of acrylic resin part is 86.
Production example 5 (synthesizing of silicone modification and acrylic resin soln)
Toward containing the silicone compounds solution that 38 parts of production examples 1 obtain, silicone compounds and 71 parts of xylol of 1 part of average group compound general formula (9) expression that is used for production example 3 and the reaction mixture that remains under 110 ℃ drip a kind of solution that contains 10 parts of methacrylic acids, 20 parts of 2-hydroxyethyl meth acrylates, 25 parts of 2-ethylhexyl methacrylic esters, 25 parts of uncle-butyl methyl acrylate and 2 parts of uncle-butyl peroxy-2-ethyl acid esters in 3 hours.Make this mixture ageing after 1 hour, in 30 minutes,, making resulting mixture ageing 2 hours then to the xylol that wherein drips 0.5 part of uncle-butyl peroxy-2-ethylhexoate and 30 parts.As a result, obtain silicone modified acrylic resin soln.Be contained in the acrylic resin modified resin that is equivalent to silicone compounds and the formation of hydroxy-containing resin bonding of silicone in this solution.In this silicone modified acrylic resin, the hydroxyl value of acrylic resin part is 86.Production example 6 (silicone modified acrylic resin soln synthetic that contains sodium salt)
Make 200 parts to mix with the ethanolic soln of 11 parts of 40wt% sodium hydroxide by the acrylic resin modified solution of production example 2 synthetic silicone.Under reduced pressure remove the solvent of this solution, residue is dissolved in the mixture of 50 parts of xylol and 50 parts of methyl iso-butyl ketone (MIBK) by distillation.Thus, obtained to contain the acrylic resin modified solution of silicone of sodium salt.Production example 7 (the acrylic resin modified solution of silicone synthetic that contains sodium salt)
The acrylic resin modified solution of 200 parts of production examples, 3 synthetic silicone is handled, to make the acrylic resin modified solution of the silicone that contains sodium salt by production example 6 same way as.Production example 8 (the acrylic resin modified solution of silicone synthetic that contains sodium salt)
The acrylic resin modified solution of 200 parts of production examples, 4 synthetic silicone is handled, to obtain a kind of acrylic resin modified solution of silicone that contains sodium salt by production example 6 same way as.Production example 9 (the acrylic resin modified solution of silicone synthetic that contains sodium salt)
200 parts of silicone modified acrylic resin solns of production example 5 synthetic are handled to obtain to contain the acrylic resin modified solution of silicone of sodium salt by production example 6 same way as.Production example 10 (the acrylic resin modified solution of silicone synthetic that contains sylvite)
The acrylic resin modified solution of 200 parts of production examples, 2 synthetic silicone is mixed with the ethanolic soln of 26 parts of 25wt% potassium hydroxide.Under reduced pressure remove solvent in this solution, residue is dissolved in the mixture of 50 parts of xylol and 50 parts of methyl iso-butyl ketone (MIBK) by distillation.Thus, obtain a kind of acrylic resin modified solution of silicone that contains sylvite.Production example 11 (the acrylic resin modified solution of silicone synthetic that contains sylvite)
The acrylic resin modified solution of 200 parts of production examples, 3 synthetic silicone is handled to obtain to contain the acrylic resin modified solution of silicone of sylvite by production example 10 same way as.Production example 12 (the acrylic resin modified solution of silicone synthetic that contains sylvite)
200 parts of silicone modified acrylic resin solns of production example 4 synthetic are handled by production example 10 same way as and obtained a kind of acrylic resin modified solution of silicone that contains sylvite.Production example 13 (the acrylic resin modified solution of silicone synthetic that contains sylvite)
The acrylic resin modified solution of 200 parts of production examples, 5 synthetic silicone is handled by production example 10 same way as and obtained a kind of acrylic resin modified solution of silicone that contains sylvite.Production example 14 (the acrylic resin modified solution of silicone synthetic that contains lithium salts)
The acrylic resin modified solution of 200 parts of production examples, 2 synthetic silicone is mixed with the ethanolic soln of 11 parts of 25wt% lithium hydroxides.Decompression is down removed solvent in this solution by distillation, and residue is dissolved in the mixture of 50 parts of xylol and 50 parts of methyl iso-butyl ketone (MIBK).Thus, obtain a kind of acrylic resin modified solution of silicone that contains lithium salts.Production example 15 (the acrylic resin modified solution of silicone synthetic that contains lithium salts)
The acrylic resin modified solution of 200 parts of production examples, 3 synthetic silicone is handled to obtain a kind of acrylic resin modified solution of silicone that contains lithium salts by production example 14 same way as.Production example 16 (the acrylic resin modified solution of silicone synthetic that contains lithium salts)
The acrylic resin modified solution of 200 parts of production examples, 4 synthetic silicone is handled to obtain a kind of acrylic resin modified solution of silicone that contains lithium salts by production example 14 identical modes.Production example 17 (the acrylic resin modified solution of silicone synthetic that contains lithium salts)
The acrylic resin modified solution of 200 parts of production examples, 5 synthetic silicone is handled, to obtain to contain the acrylic resin modified solution of silicone of lithium salts by production example 14 identical modes.Production example 18 (the acrylic resin modified solution of silicone synthetic that contains triethylamine salt)
The acrylic resin modified solution of 200 parts of production examples, 2 synthetic silicone is mixed with the ethanolic soln of 47 parts of 25wt% triethylamines.Decompression is down removed solvent in this solution by distillation, and residue is dissolved in the mixture of 50 parts of xylol and 50 parts of methyl iso-butyl ketone (MIBK).Thus, obtain to contain the acrylic resin modified solution of silicone of triethylamine salt.Production example 19 (the acrylic resin modified solution of silicone synthetic that contains triethylamine salt)
The acrylic resin modified solution of 200 parts of production examples, 3 synthetic silicone is handled to obtain to contain the acrylic resin modified solution of triethylamine salt silicone by production example 18 identical modes.Production example 20 (the acrylic resin modified solution of silicone synthetic that contains triethylamine salt)
The acrylic resin modified solution of 200 parts of production examples, 4 synthetic silicone is handled, to obtain to contain the acrylic resin modified solution of silicone of triethylamine salt by production example 18 identical modes.Production example 21 (the acrylic resin modified solution of silicone synthetic that contains triethylamine salt)
The acrylic resin modified solution of 200 parts of production examples, 5 synthetic silicone is handled to obtain to contain the acrylic resin modified solution of silicone of triethylamine salt by production example 18 identical modes.Production example 22 (synthesizing of acrylic resin soln)
In 3 hours, drip a kind of 10 parts of methacrylic acids, 20 parts of 2-hydroxyethyl methacrylic esters of containing toward containing 70 parts of xylol and remaining in the reaction mixture under 110 ℃, 25 parts of 2-ethylhexyl methacrylic esters, 25 parts of uncle-butyl methyl acrylate and 2 parts of uncle-butyl peroxy-2-ethylhexoates.After 1 hour, in 30 minutes,, make resulting mixture ageing 2 hours then at this mixture ageing to uncle-butyl peroxy-2-ethylhexoate and 30 parts of xylol of wherein dripping 0.5 part.After this, to wherein adding 20 parts of above-mentioned silicone compounds, obtain the solution of acrylic resin by average group compound general formula (7) expression.Production example 23 (acrylic resin soln synthetic that contains sodium salt)
Make 200 parts of production examples, 22 synthetic acrylic resin solns handle the solution that contains the acrylic resin of sodium salt with acquisition by production example 6 identical modes.Production example 24 (synthesizing of the acrylic resin modified solution of silicone)
Toward a kind of contain 20 parts of silicone compounds and 70 parts of xylol of representing by following average group compound general formula and remain in the reaction mixture under 110 ℃ in 3 hours the timed interval, drip a kind of solution that contains 8 parts of methacrylic acids, 20 parts of 2-hydroxyethyl meth acrylates, 27 parts of 2-ethylhexyl methacrylic esters, 25 parts of uncle-butyl methyl acrylate and 2 parts of uncle-butyl peroxy-2-ethylhexoates.At this mixture ageing after 1 hour, in 30 minutes, toward wherein dripping 0.5 part of uncle-butyl peroxy-2-ethylhexoate and 30 parts of xylol, and made the mixture ageing that obtains 2 hours.As a result, obtain the acrylic resin modified solution of silicone.Be contained in the acrylic resin modified resin that is equivalent to silicone compounds and the formation of hydroxy-containing resin bonding of silicone of this solution.
Production example 25 (the acrylic resin modified solution of silicone synthetic that contains sodium salt)
The acrylic resin modified solution of 200 parts of production examples, 24 synthetic silicone is handled by production example 6 identical modes, obtained to contain the acrylic resin modified solution of silicone of sodium salt.Production example 26 (synthesizing of the mixing solutions that hydroxy acryl acid resin and silicone are acrylic resin modified)
In 3 hours toward a kind of contain 70 parts of xylol and remain in the reaction mixture under 110 ℃ drip a kind of solution that contains 10 parts of methacrylic acids, 20 parts of 2-hydroxyethyl meth acrylates, 25 parts of 2-ethylhexyl methacrylic esters, 25 parts of uncle-butyl methyl Class C acid esters and 2 parts of uncle-butyl peroxy-2-ethylhexoates.After 1 hour, in 30 minutes,, make resulting mixture ageing 2 hours again at this mixture ageing toward wherein dripping 0.5 part of uncle-butyl peroxy-2-ethylhexoate and 30 parts of xylol.And then toward wherein adding 100 parts by the acrylic resin modified solution of production example 2 synthetic silicone.Thus, obtain hydroxy acryl acid resin and the acrylic resin modified mixing solutions of silicone.Production example 27 (contain the hydroxy acryl acid resin of sodium salt and contain the synthetic of the acrylic resin modified mixing solutions of the silicone of sodium salt)
The mixing solutions that production example 26 synthetic hydroxy acryl acid resins and silicone is acrylic resin modified is handled by production example 6 identical modes.Thus, the acrylic resin modified mixing solutions of silicone that obtains to contain the hydroxy acryl acid resin of sodium salt and contain sodium salt.Production example 28 (synthesizing of the mixing solutions that silicone compounds, hydroxy acryl acid resin and silicone are acrylic resin modified)
Toward a kind of contain 70 parts of xylol and remain in the reaction mixture under 110 ℃ in 3 hours, drip a kind of 10 parts of methacrylic acids, 20 parts of 2-hydroxyethyl meth acrylates, 25 parts of 2-ethylhexyl methacrylic esters, 25 parts of uncle-butyl methyl acrylate and 2 parts of uncle-butyl peroxy-2-ethylhexoates of containing.Make this mixture ageing after 1 hour, in 30 minutes, dripping 0.5 part of tert-butyl peroxide-2-ethylhexoate and 30 parts of xylol, and making resulting mixture ageing 2 hours to it.Add 100 parts again by the production example acrylic resin modified solution of 2 synthetic silicone and 20 parts of silicone compounds to it by above-mentioned average group compound general formula (7) expression.Thus, obtain silicone compounds, hydroxy acryl acid resin and the acrylic resin modified mixing solutions of silicone.Production example 29 (silicone compounds.Contain the hydroxy acryl acid resin of sodium salt and contain the synthetic of the acrylic resin modified mixing solutions of the silicone of sodium salt)
The mixing solutions that production example 28 synthetic silicone compounds, hydroxy acryl acid resin and silicone is acrylic resin modified is handled by production example 6 identical modes.Thus, obtain silicone compounds, contain the hydroxy acryl acid resin of sodium salt and contain the acrylic resin modified mixing solutions of silicone of sodium salt.
Example 1-16
With 18 parts of silicone by production example 6-21 synthetic metal-containing salts or amine salt acrylic resin modified with 4 parts of urethane resin linking agents " DN-950 " (by Dai-Nippon InK﹠amp; Chemicals limited-liability company produces) mix.Thus, prepare coating resin composition.To wherein adding 4 parts of xylol with preparation coating.This coating is applied on the sheet glass, and makes the sheet glass that applied at room temperature leave standstill a week to obtain cross linking membrane.
Example 17
Contain sodium salt acrylic resin and 4 parts of urethane resin linking agents " DN-950 " (by Dai-Nippon InK ﹠amp with 18 parts by production example 23 synthetic; Chemicals limited-liability company produces) mix.Thus, preparation coating resin composition.To wherein adding 4 parts of xylol with preparation coating.This coating is applied on the sheet glass, and makes the sheet glass that applied at room temperature leave standstill a week to obtain crosslinked film.
Example 18
With 18 parts by production example 25 synthetic contain the silicone of sodium salt acrylic resin modified with 4 parts of urethane resin linking agents " DN-950 " (by Dai-Nippon Ink ﹠amp; Chemicals company limited produces) mix.Thus, prepare a kind of coating resin composition.Add 4 parts of xylol with preparation coating to it.This coating is coated on the sheet glass, and makes the sheet glass of this coating at room temperature leave standstill a week to obtain cross linking membrane.
Example 19
With 18 parts contain the hydroxy acryl acid resin of sodium salt by production example 27 synthetic and contain the acrylic resin modified mixing solutions of the silicone of sodium salt and 4 parts of urethane resin linking agents " DN-950 " (by Dai-Nippon Ink ﹠amp; Chemicals company limited produces) mix.Thus, prepare coating resin composition.To wherein adding 4 parts of xylol with preparation coating.This coating is coated on the sheet glass, and makes the sheet glass that applied at room temperature leave standstill a week to obtain cross linking membrane.
Example 20
With 18 parts by production example 29 synthetic silicone resins, contain sodium salt hydroxyl acrylic resin and contain the acrylic resin modified mixing solutions of the silicone of sodium salt and 4 parts of urethane resin linking agents " DN-950 " (by Dai-Nippon Ink ﹠amp; Chemicals company limited produces) mix.Thus, prepare coating resin composition.To wherein adding 4 parts of xylol with preparation coating.This coating is coated on the sheet glass, and makes the sheet glass that applied at room temperature leave standstill a week to obtain cross linking membrane.
Comparative Examples 1-4
Use production example 2-5 synthetic silicone acrylic resin modified, obtain cross linking membrane by the method identical with example 1.Test
Make the cross linking membrane that in above-mentioned each example and Comparative Examples, obtains carry out rub(bing)test, measure contact angle, antipollution test and accelerated weathering test with water.Test and measuring method are as follows.Obtain the results are shown in table 1.[rub(bing)test]
Xylol is rubbed 100 times, again according to the state of following standard visual valuation gained film surface forward and backward by general fashion to each film.
@: do not have unusual phenomenon
Zero: almost do not have unusual phenomenon
△: film surface slightly turns white
*: film surface turn white [with the contact angle of water]
At the water droplet that drips 0.2cc on each film, measure the contact angle of this film and water droplet 1 minute the time dripping under the room temperature.[antipollution test]
Make film (stand to erode 2 years in the weathering test district of Neyagawa Jigyo-sho), from year March in March, 1991 to 1993, to check the pollution condition of this film in Nippon paint company limited.The evaluation of pollution level is by using color difference meter to measure the maximum value and the mean value of △ E value.
Judgement criteria is as described below.
@: do not pollute.
Zero: almost do not pollute.
△: light contamination.
*: pollute.
* *: significantly polluted.[accelerated weathering test]
Make film in the sunshine weatherometer through 2000 hours irradiation, so that can each resulting film surface state of visual valuation.In addition, also measured 60 ° of specular glosss, and according to the gloss retention value (%) behind the gloss measurement irradiation of pre-irradiation measurement.Visual valuation carries out according to following standard.
@: do not have unusual phenomenon
Zero: almost do not have unusual phenomenon
△: efflorescence appears in part.
*: efflorescence appears significantly.
Table 1
| Embodiment | Comparative Examples | ||||||||||||||||||||||||
| ??1 | 2 | ????3 | ????4 | 5 | ????6 | ????7 | ????8 | ??9 | ??10 | ???11 | ???12 | ???13 | ??14 | ??15 | ??16 | ??17 | ??18 | ??19 | ??20 | ??1 | ??2 | ??3 | ??4 | ||
| Produce routine number | ??6 | 7 | ????8 | ????9 | 10 | ????11 | ????12 | ??13 | ??14 | ??15 | ???16 | ???17 | ???18 | ??19 | ??20 | ??21 | ??23 | ??25 | ??27 | ??29 | ??2 | ??3 | ??4 | ??5 | |
| Rub(bing)test | ??◎ | ◎ | ????◎ | ????◎ | ○ | ????○ | ????○ | ??○ | ??○ | ??○ | ???○ | ???○ | ???◎ | ??◎ | ??◎ | ??◎ | ??◎ | ??◎ | ??○ | ??○ | ??◎ | ??◎ | ??◎ | ??◎ | |
| With water contact angle (℃) | ??58 | 57 | ????58 | ????60 | 57 | ????54 | ????58 | ??58 | ??56 | ??55 | ???58 | ???56 | ???58 | ??60 | ??60 | ??59 | ??58 | ??56 | ??62 | ??60 | ??88 | ??86 | ??89 | ??91 | |
| The antipollution test | ??◎ | ○ | ????◎ | ????△ | ○ | ????○ | ????△ | ??△ | ??◎ | ??○ | ???○ | ???○ | ???△ | ??△ | ??△ | ??△ | ??◎ | ??○ | ??○ | ??○ | ?×× | ?×× | ?×× | ?×× | |
| The accelerated weathering test | Gloss keeps | ??88 | 87 | ????90 | ????84 | 87 | ????87 | ????85 | ??84 | ??88 | ??86 | ???86 | ???85 | ???82 | ??82 | ??83 | ??83 | ??88 | ??84 | ??83 | ??83 | ??78 | ??75 | ??73 | ??75 |
| The film condition of surface | ??○ | ○ | ????○ | ????○ | ○ | ????○ | ???○ | ??○ | ??○ | ??○ | ???○ | ???○ | ???○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??△ | ??△ | |
Coating resin composition of the present invention can form has the film that improves antifouling property.Keep common necessary film performance simultaneously, for example weather-proof ability, because said composition comprises silicone compounds, hydroxy-containing resin and above-mentioned linking agent and be that form with salt exists because be contained in functional group at least a silicone compounds and the hydroxy-containing resin to small part.
When at length and consult the specific embodiment of the present invention and describe when of the present invention, the present invention can carry out various changes and improvement under without departing from the spirit and scope of the present invention, and these those skilled in the art for affiliated technical field are tangible.
Claims (6)
1, a kind of coating resin composition, it comprises
At least a silicone compounds (A) that is selected from the silicone compounds of average group compound general formula (1), (2), (3) and (4) expression,
A kind of hydroxy-containing resin (B) and
A kind of have can with the linking agent (C) of the functional group of hydroxyl reaction,
Being contained in functional group at least a described silicone compounds and the described hydroxy-containing resin to small part is that form with salt exists;
Wherein A represents at least a being selected from by chemical formula (ⅰ), (ⅱ) and (ⅲ) the organic residue in organic residue of expression:
B represents-CH
2CH
2CH
2OCH
2CH
2OH,
X represents 3-acryl propoxy-or 3-methacryloyl propoxy-,
Y represents a kind of monovalence substituting group, it contain at least a kind of being selected from-COOH ,-SO
3H and-NR
2 2(R wherein
2Be organic residue) in a group,
R
1Be aryl, aralkyl or alkyl with 1～6 carbon atom and
A, b, c and d respectively are following number of repeat unit:
1≤a≤20
0.5≤b≤3
1≤c≤10
0＜d≤6。
2, by the described coating resin composition of claim 1, wherein part silicone compounds and part hydroxy-containing resin bonding and generate silicone modified resin.
3, by the described coating resin composition of claim 1, wherein all silicone compounds and part hydroxy-containing resin bonding are to form silicone modified resin.
4, by the described coating resin composition of claim 1, wherein the hydroxyl value of hydroxy-containing resin is 20-300.
5, by the described coating resin composition of claim 1, wherein silicone compounds (A) is 3: 97-70 with the ratio of mixture ((A): (B)) of hydroxy-containing resin (B): 30 (by weight).
6, a kind of method of application of paint, this coating contains coating resin composition, and said composition comprises
Silicone compounds (A) at least a silicone compounds that is selected from average group compound general formula (1), (2), (3) and (4) expression,
A kind of resin of hydroxyl (B) and
A kind of have can with the linking agent (C) of the functional group of hydroxyl reaction,
Being contained in functional group at least a described silicone compounds and the described hydroxy-containing resin to small part is that form with salt exists;
Wherein A represents to be selected from chemical formula (ⅰ), (ⅱ) and (ⅲ) at least a organic residue in organic residue of expression:
B represents-CH
2CH
2CH
2OCH
2CH
2OH,
X represents 3-acryl propoxy-or 3-methacryloyl propoxy-,
Y represents a kind of monovalence substituting group, it contains at least one and is selected from-COOH ,-SO
3H and-NR
2 2(R wherein
2Be organic residue) in group,
R
1Be aryl, aralkyl or alkyl with 1～6 carbon atom and
A, b, c and d respectively are following number of repeat unit:
1≤a≤20
0.5≤b≤3
1≤c≤10
0＜d≤6。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12658294A JPH07331174A (en) | 1994-06-08 | 1994-06-08 | Coating resin composition |
| JP6-126582 | 1994-06-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1114334A true CN1114334A (en) | 1996-01-03 |
Family
ID=14938748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95105561 Pending CN1114334A (en) | 1994-06-08 | 1995-06-08 | Coating resin composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH07331174A (en) |
| CN (1) | CN1114334A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102892852A (en) * | 2010-04-20 | 2013-01-23 | 道康宁东丽株式会社 | Non-curable coating composition |
| CN104471004A (en) * | 2013-06-03 | 2015-03-25 | 关西涂料株式会社 | Coating composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4179323B2 (en) | 2003-01-27 | 2008-11-12 | ダイキン工業株式会社 | Paint composition |
-
1994
- 1994-06-08 JP JP12658294A patent/JPH07331174A/en active Pending
-
1995
- 1995-06-08 CN CN 95105561 patent/CN1114334A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102892852A (en) * | 2010-04-20 | 2013-01-23 | 道康宁东丽株式会社 | Non-curable coating composition |
| US8956449B2 (en) | 2010-04-20 | 2015-02-17 | Dow Corning Toray Co., Ltd. | Non-curable coating composition |
| CN104471004A (en) * | 2013-06-03 | 2015-03-25 | 关西涂料株式会社 | Coating composition |
| CN104471004B (en) * | 2013-06-03 | 2017-02-22 | 关西涂料株式会社 | Coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07331174A (en) | 1995-12-19 |
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