CN111171574B - Aqueous organic-inorganic composite resin and coating composition comprising same - Google Patents
Aqueous organic-inorganic composite resin and coating composition comprising same Download PDFInfo
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention provides an aqueous organic-inorganic composite resin and a coating composition containing the same. An aqueous organic-inorganic composite resin derived from: (A) an inorganic moiety comprising (a)1) Siloxane monomer, and (a)2) A siloxane oligomer, and (B) an organic moiety comprising (B)1) (meth) acrylic acid monomer, and (b)2) A (meth) acrylate monomer wherein (a) is2) The siloxane oligomer has the structure of formula (II): (R)5 3SiO1/2)x(R6 2SiO2/2)y(R7SiO3/2)zFormula (II) wherein R5、R6And R7Can be the same or different and are respectively and independently H, methyl, ethyl, phenyl, OH, methoxyOr ethoxy, x > 0, y > 0 and z ≧ 0, and wherein the (a) is present in an amount of the total solid content of the inorganic portion2) The siloxane oligomer is present in an amount of 25 to 60 wt%.
Description
[ technical field ] A method for producing a semiconductor device
The present invention relates to an aqueous organic-inorganic composite resin and a coating composition containing the same.
[ background of the invention ]
In recent years, photocatalysts have been used for buildings, structures and the like of buildings, and as an outdoor use, a photocatalyst is coated on a surface of a substrate to impart a function of decomposing harmful substances such as NOx and SOx with light energy to the substrate, and a so-called self-cleaning function is achieved by washing away attached dirt with rainfall on the surface of the hydrophilic layer at the time of light irradiation.
However, the oxidation characteristics of the photocatalyst may also cause deterioration of the substrate. In order to solve the above problems, a technique has been proposed in which an intermediate layer containing a silicone modified resin is provided between a photocatalyst layer and a substrate to prevent decomposition or deterioration of the substrate, but the adhesion between the silicone modified resin and the substrate is often poor.
In recent years, due to the attention of people on environmental protection, the content of Volatile Organic Compounds (VOC) in the coating is strictly controlled in various countries around the world, and the research on the coating is gradually changed from a solvent-based coating to a water-based coating. Compared with solvent-based coatings, water-based coatings have the advantages of no or low VOC content, less environmental harm, and nonflammability because water is used as a solvent. However, the aqueous coating materials are known to be inferior in terms of drying rate, water resistance, weather resistance and the like of the coating film. In addition, when particles (such as photocatalyst) are added to the coating, a dispersant is often added to help disperse the particles or to reduce the particle size by grinding to improve the dispersibility, but delamination, skinning, flocculation and the like are often observed in the ground coating.
Therefore, an environment-friendly water-based paint which has weather resistance, hydrolysis resistance, good dispersibility, storage stability and good adhesion with a substrate is continuously searched in the industry.
[ summary of the invention ]
An object of the present invention is to provide an aqueous organic-inorganic composite resin derived from:
(A) an inorganic moiety comprising (a)1) Siloxane monomer, and (a)2) Siloxane oligomer, and
(B) an organic moiety comprising (b)1) (meth) acrylic acid monomer, and (b)2) (meth) acrylic acid ester-based monomers,
wherein the (a)2) The siloxane oligomer has the structure of formula (II):
(R5 3SiO1/2)x(R6 2SiO2/2)y(R7SiO3/2)za compound of the formula (II),
wherein R is5、R6And R7Can be identical or different and are each independently H, methyl, ethyl, phenyl, OH, methoxy or ethoxy, x > 0, y > 0 and z ≧ 0
Wherein (a) is present in an amount of total weight of solids of the inorganic portion (total weight of solid contents)2) The siloxane oligomer is present in an amount of 25 to 60 wt%.
Another object of the present invention is to provide a coating composition comprising the above aqueous organic-inorganic composite resin.
In order to make the above objects, features and advantages of the present invention more comprehensible, embodiments, specific examples, etc. are described in detail below.
[ detailed description ] embodiments
To facilitate understanding of the disclosure set forth herein, several terms are defined below.
The term "about" means an acceptable error for a particular value as determined by one of ordinary skill in the art, which is based in part on how the value is measured or determined, and is generally understood to mean ± 10% of the present value.
The term "hydrocarbyl" refers to a saturated or unsaturated carbon chain group formed from hydrogen and carbon atoms, such as alkyl, alkenyl, or alkynyl groups. The hydrocarbon group may include a linear hydrocarbon group, a branched hydrocarbon group and/or a cyclic hydrocarbon group. In some casesIn an embodiment, the hydrocarbyl group may be of 1 to 30 carbon atoms (C)1-30) 1 to 25 carbon atoms (C)1-25) 1 to 20 carbon atoms (C)1-20) 1 to 15 carbon atoms (C)1-15) The carbon chain group of (1). By "alkyl" is meant a straight or branched chain saturated carbon chain group, examples include, but are not limited to, methyl, ethyl, propyl (including all isomeric forms), butyl (including all isomeric forms), pentyl (including all isomeric forms), and hexyl (including all isomeric forms). Furthermore, a hydrocarbon group may also have a-C ═ C-bond or-C ≡ C-bond and be referred to as "alkenyl" or "alkynyl".
Each mode and each embodiment of the invention disclosed in this specification can be combined with all other modes and embodiments of the invention individually, and this application covers all possible combinations.
I. Aqueous organic-inorganic composite resin
The aqueous organic-inorganic composite resin of the present invention mainly comprises (a) an inorganic silicone resin and (B) an organic acrylic resin. Through the regulation and control of the composition of the inorganic part and the organic part, the water-based organic-inorganic composite resin has weather resistance and chemical resistance, also has good flexibility and water compatibility, and can be stably stored; in addition, the inorganic particles have good dispersibility, and have good shearing resistance during grinding and dispersing of the inorganic particles. The resin coating obtained by using the water-based organic-inorganic composite resin has excellent weather resistance and good adhesion to a base material, and can solve the problems in the prior art.
According to some embodiments of the present invention, the solid content weight ratio of the inorganic portion to the organic portion is 2:8 to 8:2, such as 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, and preferably may be 5:5 to 8:2, and if the inorganic ratio is too high, precipitation is likely to occur, and if the organic ratio is too high, weatherability of the resin cannot be provided.
Inorganic part
The inorganic portion of the aqueous organic-inorganic composite resin of the present invention is a silicone resin derived from: (a)1) Siloxane monomer, and (a)2) Siloxane oligomers。
(a1) Siloxane monomers
The siloxane monomer of the present invention may be any suitable siloxane monomer, preferably a siloxane monomer having the structure of formula (I):
(R1)nSi(OR2)4-nformula (I)
Wherein R is1Each independently of the other being H, phenyl, C1-6Alkyl or an organic radical having an amino, epoxy, vinyl, isocyanate, mercapto or (meth) acryloyloxy group, R2Is C1-3Alkyl, and n is an integer from 0 to 3, such as 0, 1, 2, or 3.
In a preferred embodiment of the invention, R1Each independently is H, methyl, ethyl, vinyl, N- (. beta. -aminoethyl) - γ -aminopropyl (N- (. beta. -aminoethyl) - γ -aminopropyl), aminopropyl (aminopropyl), γ -glycidoxypropyl (γ -glycidoxypropyl), β - (3,4-epoxycyclohexyl) ethyl (β - (3,4-epoxycyclohexyl) ethyl), 3- (methacryloyloxy) propyl (3- (methacryloyloxy) propyl) or mercaptopropyl), and R is2Each independently being methyl or ethyl.
According to a more preferred embodiment of the present invention, the siloxane monomer is selected from the group consisting of trimethylmethoxysilane (trimethyoxysilane), trimethylethoxysilane (trimethyoxysilane), dimethyldimethoxysilane (dimethyldimethoxysilane), dimethyldiethoxysilane (dimethyldiethoxysilane), methyltrimethoxysilane (methyltrimethoxysilane), methyltriethoxysilane (methyltriethoxysilane), methyltripropoxysilane (methyltripropoxysilane), tetraethoxysilane (tetraethoxysilane), vinyltrimethoxysilane (vinyltrimethylsilane), vinyltriethoxysilane (vinyltriethoxysilane), gamma-glycidoxypropyltrimethoxysilane (gamma-glycidoxypropyltrimethoxysilane), gamma-glycidoxypropyltriethoxysilane (gamma-glycidoxypropyltriethoxysilane), gamma-glycidoxypropyltriethoxysilane (gamma-glycidoxypropyl), gamma-glycidoxypropyl ((gamma-glycidoxypropyl) and 3-glycidoxypropyl-methyldiethoxysilane (gamma-glycidoxypropyl), 4-epoxycyclohexyl) ethyltrimethoxysilane (beta- (3,4-epoxycyclohexyl) ethyl trimethoxysilane), 3- (methacryloyloxy) propyltrimethoxysilane (3- (methacryloyloxy) propyltrimethoxysilane), N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane (N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane), N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (N- (beta-aminoethyl) -gamma-aminopropylmethyldiethoxysilane), gamma-aminopropylmethyldiethoxysilane (gamma-aminopropyltriethoxysilane), gamma-aminopropyltriethoxysilane (gamma-aminopropyltrimethoxysilane), gamma-aminopropyltrimethoxysilane (gamma-aminopropyltrimethoxysilane), gamma-aminopropyltriethoxysilane (gamma-aminopropyltrimethoxysilane), and combinations of any of the foregoing Group (2): .
According to some embodiments of the invention, (a) is based on the total solids weight of the inorganic portion1) The siloxane monomer is present in an amount of 40 wt% to 75 wt%, for example 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt% or 75 wt%.
(a2) Siloxane oligomers
Generally, silicone resins are easy to be hard and brittle after film formation, and the common solution is to add a D-Type (D-Type) siloxane monomer to increase the proportion of linear structures in the silicone resin to make it flexible. However, even in the case of using the D-Type siloxane monomer, there is a problem that it is difficult to control the degree of linear polymerization when the various siloxane monomers are directly blended for polymerization, and the improvement effect is limited. The inorganic part of the invention contains siloxane oligomer, can adjust the properties of the coating composition after curing, provides good toughness and anti-shrinkage property, enables the film forming property of the coating film to be good, and can improve the properties of dispersion and the like of inorganic particles.
According to some embodiments of the invention, the siloxane oligomer has the structure of formula (II):
(R5 3SiO1/2)x(R6 2SiO2/2)y(R7SiO3/2)zformula (II)(II)
Wherein R is5、R6And R7Can be the same or different and are each independently H, methyl, ethyl, phenyl, OH, methoxy or ethoxy, x is more than 0, y is more than 0, and z is ≧ 0; preferably, 23 > x > 0, 22 > y > 0 and 30 > z ≧ 0. The invention uses the siloxane oligomer prepared in advance to polymerize with the siloxane monomer, thereby being easy to regulate and control the linear structure proportion in the siloxane resin and being beneficial to controlling the property of the composite resin.
According to some embodiments of the invention, the polysiloxane oligomer is a linear structure having the formula (III):
wherein each R3May be the same or different and are each independently methyl or phenyl; each R4May be the same or different and are each independently H, methyl or ethyl; and m is an integer from 2 to 20, such as 2, 3, 5, 10, 15, or 20.
According to some embodiments of the present invention, the siloxane oligomer has a weight average molecular weight of 500 to 5000, for example 500, 800, 1000, 1500, 2000, 3000, 4000 or 5000, preferably may have a weight average molecular weight of 800 to 3000, more preferably may have a weight average molecular weight of 1000 to 2000. The molecular weight of the siloxane oligomer affects the operability of the coating composition prepared: when the molecular weight is too high (for example, when the weight average molecular weight is more than 5000), the prepared organic-inorganic composite resin has poor water solubility and is easy to precipitate; when the molecular weight is too low (for example, when the weight average molecular weight is less than 500), the prepared organic-inorganic composite resin is too hard and brittle to cause easy cracking of the coating layer and the substrate.
The inventors of the present application found that by adding an appropriate amount of siloxane oligomer (e.g., 25 wt% or more), the obtained organic-inorganic composite resin has good abrasion processing resistance, and the obtained coating layer has good flexibility, weather resistance, and good adhesion to a substrate. According to some embodiments of the invention, (a) is based on the total solids weight of the inorganic portion2) The siloxane oligomer is present in an amount of 25 wt.% to 60 wt.%, e.g., 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, or 60 wt.%. When the content of the siloxane oligomer is too low (e.g., less than 25% by weight), the coating is insufficient in flexibility, too hard and brittle, resulting in easy cracking of the coating and the substrate and poor weather resistance, and furthermore, the resulting organic-inorganic composite resin is not resistant to abrasive processing; conversely, if the content of the siloxane oligomer is too high (e.g., more than 60 wt%), the water solubility of the resin and the workability of the grinding process are impaired.
Organic moieties
The organic portion of the aqueous organic-inorganic composite resin of the present invention is an acrylic resin derived from: (b)1) (meth) acrylic acid monomer, and (b)2) (meth) acrylate monomers.
(b1) (meth) acrylic acid monomer
The organic portion of the present invention comprises (meth) acrylic monomers, i.e., acrylic acid and/or methacrylic acid. Since the resulting organic-inorganic composite resin has a carboxyl group derived from a (meth) acrylic monomer, the resulting resin is soluble in water or hydrophilic. The incorporation of an appropriate amount of (meth) acrylic monomer (e.g., 5 wt% or more) in the organic portion can further increase the water solubility of the organic-inorganic composite resin, help the storage stability of the coating, and provide adhesion of the resin to the substrate. According to some embodiments of the invention, the (b) is based on the total solid weight of the organic portion1) The amount of (meth) acrylic monomer is 5 wt% to 25 wt%, such as 5 wt%, 10 wt%, 15 wt%, 20 wt% or 25 wt%. If the content of the acrylic monomer is too high, the water resistance and weather resistance of the organic-inorganic composite resin are deteriorated; conversely, if the acrylic monomer content is too low, the organic-inorganic composite resin cannot be uniformly dispersed in an aqueous phase to prepare an aqueous resin, and the adhesion of the resin to a substrate is also deteriorated.
(b2) (meth) acrylic acid ester monomer
The organic moiety of the present invention comprises, in addition to the (meth) acrylic monomer, a (meth) acrylate monomer, wherein the ester end of the (meth) acrylate monomer may be connected to a hydrocarbon group, such as an alkyl group, an alkenyl group, or an alkynyl group. According to a preferred embodiment of the present invention, the aforementioned hydrocarbyl group linking the ester ends may be an alkyl group, which may be linear, branched or cyclic, optionally substituted (e.g. by hydroxyl), and may have 1 to 30 carbon atoms, for example 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25 or 30 carbon atoms, preferably 2 to 20 carbon atoms. The alkenyl and alkynyl groups are as described above for alkyl groups, except that they have a minimum of 2 carbon atoms.
According to one embodiment of the present invention, the (b)2) The (meth) acrylate-based monomer comprises a monomer of formula (IV):
wherein A is C having a hydroxyl group2To C6Alkylene radical, R8Is H or methyl, and R9、R10And R11Each independently is C1To C8An alkyl group.
According to one embodiment of the present invention, in formula (IV), A is C having a hydroxyl group2To C6Alkylene, wherein the hydroxyl group is preferably a primary hydroxyl group or a secondary hydroxyl group (i.e., a has a branched structure); r8Is H or methyl; r9Is methyl; and R10And R11The total number of carbon atoms of (a) is 3 to 9. In some embodiments of the invention, R in formula (IV)10And R11The sum of the number of carbon atoms of (a) is from 4 to 8, for example 5, 6 or 7.
C above2To C6Specific examples of alkylene groups include, but are not limited to, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, pentylene, and hexylene. C1To C8Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptylAlkyl, neoheptyl, n-octyl, and isooctyl.
According to some embodiments of the invention, the monomer of formula (IV) is present in an amount of 5 wt% to 30 wt%, such as 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%, preferably 10 wt% to 25 wt%, based on the total solids weight of the organic portion.
The monomer of formula (IV) is prepared by, but not limited to, reacting tertiary carboxylic acid glycidyl esters (tertiary carboxylic acid glycidyl esters) with (meth) acrylic acid, for example, by reacting C5To C13Obtained by reacting a glycidyl ester of a novel carboxylic acid with (meth) acrylic acid, or by reacting a glycidyl (meth) acrylate with C5To C13New carboxylic acid is obtained by reaction. C5To C13Specific examples of the glycidyl ester of a neocarboxylic acid include, but are not limited to, glycidyl pivalate, glycidyl neoheptanoate, glycidyl neononanoate, glycidyl neodecanoate, glycidyl neoundecanoate, and glycidyl neotridecanoate. C5To C13Specific examples of the novel carboxylic acid include, but are not limited to, pivalic acid, neoheptanoic acid, neononanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and neotridecanoic acid. According to some embodiments of the invention, the monomer having formula (IV) may be obtained by the above reaction.
The monomer of formula (IV) is a copolymerizable monomer having a pendant hydroxyl group in the middle portion of the structure of formula (IV) (i.e., the carbon atom bonded to A) rather than being bonded to the terminal end of the structure of formula (IV), e.g., R, and an ethylenic bond9、R10And R11To (3). In this case, the monomer of formula (IV) has both a quaternary carbon structure and a pendant hydroxyl group. By using the monomer of formula (IV) having a quaternary carbon structure and a pendant hydroxyl group in the middle in the organic moiety, the durability of the resin can be further improved, and the water solubility of the organic-inorganic composite resin can be increased.
According to some embodiments of the present invention, examples of the monomer having formula (IV) include, but are not limited to, at least one selected from the following formulae (IV-1) to (IV-3):
in the formulae (IV-1) to (IV-3), R10And R11Each independently is C1To C8Alkyl, and R10And R11The sum of the number of carbon atoms of (a) is from 3 to 9, more particularly from 4 to 8, for example 5, 6 or 7.
In addition to (b) applicable to the present invention2) The (meth) acrylate monomer is selected from, for example, but not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, hexyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isobutyl (meth) acrylate, 2-butyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, isotridecyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and stearyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and combinations of any two or more of the foregoing.
Preparation of aqueous organic-inorganic composite resin
The aqueous organic-inorganic composite resin of the present invention is formed by synthesizing an inorganic silicone resin, and then copolymerizing the inorganic silicone resin with an organic moiety monomer ((meth) acrylic acid monomer, (meth) acrylic acid ester monomer, and optionally other monomers).
According to some embodiments of the invention, the silicone resin of the invention is synthesized in a sol-gel (sol-gel) process. Other compounds may be added as raw materials without significantly affecting the object of the present invention or the technical effect of the present invention. In a typical sol-gel process, the reactants undergo a series of hydrolysis and polymerization reactions to form a colloidal suspension, and the materials therein coagulate into a new phase: a solution containing a solid polymer, i.e., a gel.
According to some embodiments of the present invention, a solvent including, but not limited to, alcohols, alcohol ethers, or a mixture thereof may be added as needed in the sol-gel synthesis step. Non-limiting examples of alcoholic solvents include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, or the like. Non-limiting examples of the alcohol ether-based solvent include ethylene glycol monobutylether (BCS), ethylene glycol monoethyl ether acetate (CAC), ethylene glycol monoethyl Ether (ECS), propylene glycol monomethyl ether (propylene glycol monomethyl ether), propylene glycol monomethyl ether acetate (PMA), propylene glycol monomethyl ether propionate (PMP), or a mixture thereof.
According to a preferred embodiment of the present invention, the method for producing an aqueous organic-inorganic composite resin according to the present invention may comprise the steps of:
(1) provision of inorganic moieties
Will be as described hereinbefore (a)1) Siloxane monomer, and (a)2) The siloxane oligomer having the structure of formula (II) is mixed and reacted at an appropriate temperature with the addition of a catalyst (for example, by heating at 60 to 90 ℃ for 4 to 8 hours) to form a transparent sol-gel having good fluidity. The above catalyst is not particularly limited, and any suitable catalyst generally used for synthesizing silicone resins by a sol-gel method may be used, and an acidic catalyst, such as citric acid, hydrochloric acid, and acetic acid, is preferable.
(2) Provision of organic moieties
Providing one or more of (b)1) (meth) acrylic acid monomer, and (b)2) (meth) acrylate monomers.
In one embodiment of the present invention, (b) is adjustable1) And (b)2) The type and amount of the monomer are such that the overall resin has water solubility and good adhesion to the substrate.
(3) Compounding of inorganic and organic moieties
The inorganic portion and the organic portion are mixed and reacted at a solid content weight ratio of 8:2 to 2:8 (which may be 7:3 to 3:7, or 6:4 to 4:6), and if necessary, a common additive (such as a coupling agent, an initiator, etc.) is added, and a copolymerization reaction is performed at an appropriate temperature (for example, heating at 60 ℃ to 100 ℃ for 2 to 8 hours) to form an organic-inorganic composite resin. If necessary, an initiator and/or a solvent may be further added, and the reaction may be repeated to complete the curing.
The same or different solvents (e.g., alcohols, alcohol ethers or mixtures thereof) may be added as necessary in any of the above steps (1) to (3). Examples of the alcohol, alcohol ether solvent are as described above. It is preferred to add an alcoholic solvent such as, but not limited to, methanol, ethanol, propanol, butanol, isopropanol, isobutanol, ethylene glycol, propylene glycol or mixtures thereof.
The coupling agents which may be added as required in step (3) above are those known to the person skilled in the art, such as 3- (methacryloyloxy) propyltrimethoxysilane, which consists of two parts: a part is an inorganic group which can react with the silicone resin; the other part is an organophilic group which is reactive with acrylic resins.
The initiator which may be added to the above step (3) as required is a substance well known to those skilled in the art, and is exemplified by, but not limited to, benzene peroxide, dicumyl peroxide, butyl hydroperoxide, cumene hydroperoxide, tert-butylmaleic peroxide, tert-butyl peroxy-2-ethylhexanoate (TBPO), tert-butyl hydroperoxide, acetyl peroxide, lauroyl peroxide, Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, a mixture of a peroxide and a sulfonic acid, a mixture of a peroxide and a cobalt compound, or a mixture of two or more of the above, preferably azobisisobutyronitrile or tert-butyl peroxy-2-ethylhexanoate.
II, application of water-based organic-inorganic composite resin
The water-based organic-inorganic composite resin has good storage stability, water solubility and processability, has good dispersibility to inorganic particles, and can be applied to photocatalyst (such as titanium dioxide) finish paint because the obtained coating has weather resistance and hydrolysis resistance and good adhesion to a coated substrate. Conventionally, a resin used for a photocatalyst coating material cannot withstand high shear force (shear force) and long-term grinding (grinding), and a photocatalyst is not easily dispersed in the coating material, and therefore, a dispersant is often required to be added. The physical property of the coating can be influenced by too much addition amount of the dispersing agent; the amount of the dispersant added is too small, and the dispersing effect is not good. In addition, when the dispersant is added to the resin, the dispersion characteristics may be changed by the influence of the resin, so that the photocatalyst is not easily distributed on the surface of the coating layer, thereby reducing the efficacy of the photocatalyst.
The aqueous organic-inorganic composite resin of the present invention can withstand a process of grinding and dispersing inorganic particles for a long time without disintegration by adding an appropriate siloxane oligomer (25 wt% or more based on the total weight of solid matters of the inorganic part) at the time of synthesizing the inorganic part, has excellent high shear processing resistance, has high dispersibility to photocatalyst particles, can uniformly disperse the photocatalyst particles, and suspends the photocatalyst particles on the surface of a coating layer to provide a better photocatalytic effect, so that the aqueous organic-inorganic composite resin of the present invention can be used for a photocatalyst coating material. In addition, the aqueous organic-inorganic composite resin has good adhesion to a substrate and weather resistance, can be applied to a photocatalyst coating and an intermediate layer of the substrate, and can improve the substrate degradation caused by the oxidation characteristic of the photocatalyst.
The aqueous organic-inorganic composite resin of the present invention is soluble in water or hydrophilic due to having a carboxyl group derived from a (meth) acrylic monomer. Even if an organic solvent is used for resin synthesis, the oil phase can be changed into the water phase after the synthesis, and an aqueous solvent can be used to replace the organic solvent. Therefore, compared with the prior art, the invention can effectively reduce the VOC content so as to reduce the volatility, the inflammability, the environmental impact, the harm to human bodies and the like of the solvent.
Coating composition
The present invention also relates to a coating composition comprising the above aqueous organic-inorganic composite resin, preferably an aqueous coating composition. According to some embodiments of the present invention, the aqueous organic-inorganic composite resin is present in an amount of 3 wt% to 35 wt%, for example 5 wt%, 7 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%, preferably between 5 wt% and 30 wt%, based on the total weight of the composition.
The coating composition of the present invention may contain any solvent and additive known to those skilled in the art as necessary, and the kind of the additive is not limited to, for example, a neutralizer, a hardener, an accelerator, a surfactant, inorganic particles, a dispersant, an antifoaming agent, an antioxidant, a matting agent, a thixotropic aid, a stabilizer, a leveling agent, a wetting agent, an adhesion promoter, an antistatic agent, a coloring material, a filler, an ultraviolet absorber, a heat dissipation aid, a photocatalyst or an anti-floating agent, or a mixture of any two or more of the above.
Solvent(s)
The coating composition of the present invention can be adjusted in coatability by adding an appropriate amount of a solvent as needed. The solvent which can be used in the coating composition of the present invention is not particularly limited in principle, and may be an appropriate solvent well known to those skilled in the art. According to some embodiments of the present invention, the solvent used in the coating composition may be selected from water or other solvents that are more miscible with water, such as alcohols or alcohol ethers, preferably alcohols, for environmental protection. Examples of the alcohol, alcohol ether solvent are as described above. For example, the solvent used for the coating composition may be water, a mixed solution of water and alcohols, a mixed solution of water and alcohol ethers, or a mixed solution of water, alcohols, and alcohol ethers.
According to some embodiments of the invention, the solvent is present in an amount between 50 wt% and 90 wt%, such as 50 wt%, 60 wt%, 70 wt%, 80 wt% or 90 wt%, based on the total weight of the composition.
Neutralizing agent
The coating composition of the present invention may be prepared by adding a neutralizing agent to the aqueous organic-inorganic composite resin of the present invention after the synthesis thereof, if necessary, dissociating the carboxyl group contained in the resin with the neutralizing agent to generate hydrogen ions and carboxylate ions, thereby increasing the water solubility of the resin, and adding water or other solvent having a good water-solubility to the resin to prepare an aqueous resin composition or an aqueous coating composition. Neutralizing agents suitable for use in the present invention should be proton (hydrogen ion) accepting materials such as metal hydroxides, metal carbonates or ammonia or amine compounds. Non-limiting examples of metal hydroxides include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, or the like. Non-limiting examples of metal carbonates include sodium carbonate, sodium bicarbonate, or the like. Non-limiting examples of ammonia or amine compounds include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, aniline, dimethylaniline, ethylenediamine, ethanolamine or the like. According to a preferred embodiment of the present invention, ammonia is used as the neutralizing agent.
According to some embodiments of the invention, the neutralizing agent is present in an amount between 0.1 wt.% and 5 wt.%, e.g., 0.1 wt.%, 0.2 wt.%, 0.5 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.% or 5 wt.%, preferably between 0.5 wt.% and 2.5 wt.%, based on the total weight of the composition solids.
Surface active agent
The present invention can use a surfactant according to need, the surfactant is not limited to a reactive surfactant or a non-reactive surfactant, preferably a reactive emulsifier, the reactive emulsifier of the present invention includes but is not limited to an anionic reactive emulsifier and a non-ionic reactive emulsifier, and specific examples of the anionic reactive surfactant include alkyl ethers such as AQUARON series manufactured by first industrial pharmaceutical company, ADEKA soap/SR series manufactured by asahi electro chemical company, LATEMUL PD-104 manufactured by kawa; sulfosuccinates such as LATEMUL S-series manufactured by Kao corporation and ELEMINOL JS-2 manufactured by Sanyo chemical Co., Ltd; alkylphenyl ethers or alkylphenyl esters, such as AQUARON H-2855A, H-3855B, H-3855C, H-3856, HS-05, HS-10, HS-20, HS-30, BC-05, BC-10, BC-20, manufactured by Asahi Denka corporation, ADEKA REASOAP SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, and SE-10N, SE-20N; (meth) acrylate sulfates such as Antox MS-60 and MS-2N manufactured by Nippon emulsifier Co., Ltd., ELEMINOL RS-30 manufactured by Sanyo chemical industries, Ltd.; examples of the phosphoric acid compounds include H-3330PL manufactured by first Industrial pharmaceutical Co., Ltd, and ADEKA REASOAP PP-70 manufactured by Asahi Denka Co., Ltd. Examples of the nonionic reactive surfactant include alkyl ethers such as ADEKA REASOAP ER-10, ER-20, ER-30 and ER-40 manufactured by Asahi Denka Co., Ltd., LATEMULPD-420, PD-430 and PD-450 manufactured by Kao corporation; alkylphenyl ethers or alkylphenyl esters, for example AQUARON RN-IO manufactured by first Industrial pharmaceutical Co.
Inorganic particles
According to some embodiments of the present invention, the coating composition may optionally comprise inorganic particles, which may have a photocatalytic effect. According to a preferred embodiment of the present invention, the inorganic particles are selected from the group consisting of titanium dioxide, zirconium oxide, silicon dioxide, zinc oxide, strontium titanate, indium tin oxide, antimony tin oxide, lanthanum hexaboride, tungsten oxide, and a combination of any two or more of the foregoing. The order of addition and timing of addition of the inorganic particles are not particularly limited, that is, the components may be mixed with the resin of the present invention at once, in batches, or in any order, and may be added at the time of preparing the resin of the present invention or after the preparation of the resin of the present invention.
The amount of the inorganic particles to be added is not particularly limited, and may be adjusted depending on the use and desired characteristics of the coating composition. According to some embodiments of the invention, the inorganic particles are present in an amount of between 0 wt% and 60 wt%, such as 1 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt% or 60 wt%, preferably between 20 wt% and 45 wt%, based on the total composition solids.
In general, when inorganic particles are added to a coating composition, the particles are finely divided by stirring and grinding (e.g., mechanical ball milling) and uniformly dispersed in the coating composition. However, acrylic resins generally cannot withstand high shear forces and long-term grinding. Different from the prior art, the proportion of linear structures in the resin can be increased by using the siloxane oligomer, the content of the siloxane oligomer can be regulated, and the obtained resin has high shear force processing resistance, good storage stability, adhesion, chemical resistance and weather resistance, has high dispersibility to inorganic particles, and can effectively improve the problems in the prior art.
Use of coating compositions
As described above, the aqueous organic-inorganic composite resin of the present invention has many excellent properties, such as high shear processing resistance, water solubility, storage stability, adhesion, chemical resistance, weather resistance, high dispersibility to inorganic particles, and the like, and can be prepared into a coating composition by adding various additives as needed.
The coating composition of the present invention may be applied directly onto a substrate to form a coating layer, and the application method may be any method known to those skilled in the art, such as, but not limited to: knife coating, brush coating, flow coating, dip coating, spray coating, slot coating, spin coating, and curtain coating. The coating composition can be coated on a substrate for protection, scratch resistance, impact resistance, weather resistance, reflection, heat insulation or cleaning, and has the properties of water resistance, durability and the like. Examples of the substrate include, but are not limited to: metal substrate, plastic substrate, glass substrate, wall or building outer wall.
According to one embodiment of the present invention, the coating composition of the present invention is used for exterior walls of buildings, metal substrates for buildings, glass substrates for buildings, or the like, and must be exposed to outdoor environments for a long period of time, and thus moisture and dirt are easily accumulated in the environment, resulting in an unclean appearance or poor light utilization. According to a preferred embodiment of the present invention, inorganic particles having a photocatalytic effect (such as titanium dioxide) may be added to the coating composition of the present invention. For example, titanium dioxide has a function of absorbing light to excite electrons, and thus has photocatalytic properties. After the titanium dioxide is excited by light, moisture molecules or oxygen molecules in the air are activated to form hydroxyl radicals or negative oxygen ions, and the redox effect is performed to decompose pollutants in the environment, so that the pollutants in the air can be removed, and the effects of resisting pollution and self-cleaning are achieved.
In addition, the oxidation characteristics of titanium dioxide also directly cause deterioration of the substrate. A common solution to this problem is to embed an interposer between the substrate and the titanium dioxide photocatalyst layer (topcoat), but this approach increases processing complexity if the resins used for the titanium dioxide photocatalyst layer and the interposer are different.
The inorganic part of the aqueous organic-inorganic composite resin has excellent dispersibility for titanium dioxide, and has excellent weather resistance and chemical resistance, and the deterioration of a substrate is avoided. In addition, the organic part of the water-based organic-inorganic composite resin has good adhesion with a substrate, so that the coating composition prepared from the water-based organic-inorganic composite resin can be simultaneously applied to forming a photocatalyst finish as a top coating to prevent dust on the outer wall of a building, or forming an intermediate layer without a photocatalyst between the substrate and the finish coating to prolong the service life of the substrate.
Examples
The following examples are intended to further illustrate the invention but are not intended to limit the scope of the invention in any way. Any modifications and variations that may be easily accomplished by a person skilled in the art are intended to be included within the scope of this disclosure and the appended claims.
Preparation of aqueous organic-inorganic composite resin
In a reaction kettle, isopropanol is used as a solvent, and (a) is respectively added1) And (a)2) Mixing and stirring the components according to a set ratio (shown in tables 1 and 2, and the using amount of the reactants in the tables is expressed by weight percent), introducing nitrogen, and heating and reacting at 60-80 ℃ for 4-8 hours to prepare the silicone resin.
Then the obtained silicone resin and (b)1) And (b)2) Mixing and stirring the components according to the set weight ratio (shown in tables 1 and 2), introducing nitrogen, and heating and reacting at 60-80 ℃ for 4-8 hours to form the water-based organic-inorganic composite resin.
TABLE 1
TABLE 2
Note 1: prepared by reaction of methacrylic acid and glycidyl neodecanoate
Preparation of the coating composition
The organic-inorganic composite resin containing isopropyl alcohol (solid content: 50%) prepared in the above preparation examples 1-1 to 1-6 and 2-1 to 2-5 was mixed with a neutralizer and water, and stirred uniformly to prepare the aqueous coating composition of the present invention, under the preparation conditions shown in table 3:
TABLE 3
Preparation of the coating
The coating composition prepared above was applied to a 1mm glass plate using a No. 22 applicator, and baked under curing conditions of 60 ℃ for 1 minute, to give a coating film having a thickness of about 4 μm to about 5 μm.
Physical Property test
The coating composition and the coating film were subjected to various tests including resin storability, water solubility, processability, dispersibility, coating film adhesion, coating film water resistance and coating film durability. The various tests are detailed below:
storage property: the resin is sealed and kept still for 14 days at 50 ℃, and the viscosity is measured, wherein the viscosity is preferably less than 100cps, and is not good if the viscosity is more than 500 cps.
Water solubility: the aqueous coating composition prepared in table 3 was filled in an appropriate glass container in an amount of 0.5L, sealed and put in a 50 ℃ oven, taken out after 14 days and left at room temperature for 1 day, and then observed for the presence of delamination, skinning and flocculation of the resin.
Processability: 1000g of the aqueous coating composition was added with 50g of photocatalyst titanium dioxide, and the mixture was ground for 3 hours by a bead mill filled with zirconium beads having a diameter of 0.1mm (filling rate: 80% of the total volume), and the ground liquid was taken out and left to stand at room temperature for 1 day to observe whether or not there were any delamination, skinning and flocculation.
Dispersibility: in the same way as the preparation method of the processability, the grinding fluid after grinding for 3 hours is diluted with 100 times of water, and the particle size is measured by using a Dynamic Light Scattering (DLS) instrument, wherein the particle size is optimally less than 100nm, the next time is 100-200 nm, the worse is 200-500 nm, and the worst is more than 500 nm.
Coating film adhesion: and scraping the coating film on the surface of the coating film by a hundred-grid scraper, then sticking the coating film by an adhesive tape, tearing the coating film at 90 degrees, and judging the number of the stripped grids.
And (3) water resistance of the coating: the coating film was immersed in distilled water or deionized water for 7 days to confirm whether whitening or peeling occurred in the coating film.
Durability of the coating film: the accelerated aging tester QUV is used for measuring the light source wavelength of 340nm and the illumination intensity of 1W/m2Under the conditions (2), the deterioration of the coating film surface with time was observed.
Test results
The results of the relevant tests for each example and comparative example are shown in table 4:
TABLE 4
Remarking:
excellent as
Good indication
Delta denotes the common
X represents a difference
As is clear from table 4, the aqueous organic-inorganic composite resin of the present invention is excellent in various performances, and has good resin storability, water solubility, processability, dispersibility, coating adhesion, coating weather resistance, coating water resistance and coating durability.
On the contrary, if the content of carboxyl groups in the aqueous organic-inorganic composite resin is too low (as in comparative example 2-1), the water solubility of the resin is deteriorated and the storage property, processability, dispersibility, coating adhesion, coating water resistance, coating durability and other properties of the resin are simultaneously affected; if the carboxyl group content in the aqueous organic-inorganic composite resin is too high (as in comparative example 2-2), the water resistance and durability of the coating film are insufficient; if the siloxane oligomer content is too low (as in comparative examples 2-3), the coating layer has poor adhesion to the substrate and is prone to cracking; if the siloxane oligomer content is too high (as in comparative examples 2-4), the water solubility of the resin will be poor; on the other hand, if the content of the structure of formula (IV) is too low (as in comparative examples 2 to 5), the durability of the coating film is insufficient.
Claims (6)
1. An aqueous organic-inorganic composite resin derived from:
(A) an inorganic moiety comprising (a)1) Siloxane monomer, and (a)2) Siloxane oligomer, and
(B) an organic moiety comprising (b)1) (meth) acrylic acid monomer, and (b)2) (meth) acrylic acid ester-based monomers,
wherein the (a)2) The siloxane oligomer has the structure of formula (III):
wherein each R3May be the same or different and are each independently methyl or phenyl; each R4May be the same or different and are each independently H, methyl or ethyl; and m is an integer of 2 to 20,
wherein the (b)2) The (meth) acrylate-based monomer comprises a monomer of formula (IV):
wherein A is C having a hydroxyl group2To C6Alkylene radical, R8Is H or methyl, and R9、R10And R11Each independently is C1To C8Alkyl radical
And the number of the first and second electrodes,
wherein the (a) is based on the total solid content weight of the inorganic portion2) The content of siloxane oligomer is 25 to 60 wt%; wherein (b) is based on the total solid weight of the organic portion1) The content of (meth) acrylic acid monomer is 5 to 25 wt%; the content of the monomer of formula (IV) is 5 to 30 wt%; and the weight ratio of the solids content of the inorganic portion to the organic portion is from 2:8 to 8:2,
wherein the (a)1) The siloxane monomer has the structure of formula (I):
(R1)nSi(OR2)4-na compound of the formula (I),
wherein R is1Each independently of the other being H, phenyl, C1-6Alkyl or an organic radical having an amino, epoxy, vinyl, isocyanate, mercapto or (meth) acryloyloxy group, R2Is C1-3Alkyl, and n is an integer of 0 to 3.
2. The aqueous organic-inorganic composite resin according to claim 1, wherein R is1Is H, methyl, ethyl, vinyl, N- (. beta. -aminoethyl) -. gamma. -aminopropyl,. gamma. -glycidoxypropyl,. beta. - (3,4-epoxycyclohexyl) ethyl, 3- (methacryloyloxy) propyl or mercaptopropyl, and R2Is methyl or ethyl.
3. The aqueous organic-inorganic composite resin according to claim 1, wherein the (a) is2) The siloxane oligomer has a weight average molecular weight of 500 to 5000.
4. The aqueous organic-inorganic composite resin according to claim 1, wherein A in the monomer of formula (IV) is C having a primary hydroxyl group or a secondary hydroxyl group2To C6Alkylene radical, R9Is methyl, and R10And R11The total number of carbon atoms of (a) is 3 to 9.
5. A coating composition comprising the aqueous organic-inorganic composite resin according to any one of claims 1 to 4.
6. The coating composition of claim 5, further comprising inorganic particles, wherein the inorganic particles are selected from the group consisting of titanium dioxide, zirconium oxide, silicon dioxide, zinc oxide, strontium titanate, indium tin oxide, antimony tin oxide, lanthanum hexaboride, tungsten oxide, and combinations of any two or more of the foregoing.
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