JPS59501165A - Autoxidizable aqueous dispersion - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Autoxidizable aqueous dispersion The invention has use in surface coatings and adhesives. [IJ Mama - Aqueous Dispersion and even more particularly in dispersions where the particles contain autoxidizable polymers. related.

Autoxidizable polymers, i.e. polymers that crosslink on exposure to oxygen, It has been known for many years and has been widely used in the surface coating industry. It is something. The most commonly used autoxidizable species are naturally occurring triglycerides - long chain unsaturated fatty acids derived from drying oils; other autoacids Species that can be converted into (butanoene) and certain ant/butanyl group-containing substances, but the drying oil-induced appearance is the conventional amount. has also been widely used.

It has been pursued by the surface coating industry for many years. To achieve this goal, many Numerous attempts have been made. One typical method is to use a highly water-solubilized solution with a base. The aim was to produce an alkyd resin with a high price. However, this system 1) The original promise of this system could not be realized.

A newer method is the use of ethylene-based Conventional alkyd resin in water with the help of nonionic surfactants with heavy bonds It is a dispersion of. In this way, if a film is formed, the surfactant The alkyd resin method uses iodine where the ethylene double bond is allyl. It is described in Roppa Patent Application Publication No. 0002252.

Another way to achieve an aqueous autoxidizable coating composition is to The aim was to utilize autoxidizable polymers as one component of the polymer particles.

"Multipolymer particles" means film-forming particles containing at least two polymers. remer particles, and these polymers (“in-the-same polymers”) ) is at least one other polymer (“preformed polymer”) formed in the presence of This creates a homogeneous physical mixture of several different polymers. and blends of polymers, depending on the materials used, or between polymers. A blend is produced in which a slight reaction occurs. Such a dispersion It offers considerable flexibility in the formation of coating compositions. This dispersion has several types. It is often possible to obtain coating films with the advantageous properties of make it possible. Tonoyo 3 A common method for making eel particles is to combine at least one preformed polymer with ethylene. dispersion or dispersion in a system of unsaturated monomers, thus formed@ Dispersing the liquid in water and then polymerizing the monomers to form multipolymer particles in water. The first step is to form a liquid dispersion. An example of such a multi-two-lima-one particle is, for example, , UK Patent Nos. 1417713, 14211142 and 1515723 and can be found in Yokoa Patent Application Publication No. 0010424.

in the same system in the presence of a preformed polymer to create an autoxidizable dispersion. An example of an attempt to use the multi-f IJ mom-child method to form a rimmer: -f, , U.S. Patent No. 362, which blends alkyd long fat with ethylenically unsaturated monomers. No. 0989.

In this patent, alkyd resins have ethylenic unsaturation and are carefully combined with monomers. Copolymerized. However, this polymerization has an insufficient conversion rate and thus 4. Undesirably high concentrations of free monomer in the resulting coating composition. give.

Satisfactory implementation as a film-forming component of autoxidizable coating compositions It is possible to produce aqueous dispersions of particles suitable for use with I have now found out what to say.

According to the invention, therefore, an aqueous dispersion of film-forming polymer particles comprising: The particles contain at least one compound containing at least two autoxidizable groups. and polymers formed by addition polymerization of ethylenically unsaturated monomers; The dispersion further comprises at least one stabilizing compound for the particle suspension. An autoxidizable film-forming material comprising a liquid, (a) at least two of the autoxidizable groups have the formula CH2=CR-CH2-0 - (wherein R is H or CH3), (b) the material of the dispersed particles contains 02-35% by weight of the autooxidizable group; <C) said group is at least the total number of autoxidizable groups present in the material of the particle and (d) when the stabilizing compound is amphiphilic, an ethylene-based Contains no unsaturations A material is provided that is characterized by:

Further, the autoxidizable film-forming material is further comprised of (a) a monomer and at least a compound containing two autoxidizable groups, water, and a stabilizing compound forming a mixture; and (b) polymerizing the monomer to form a film-forming aqueous dispersion of particles of the polymer; A method for manufacturing a process comprising: (c) at least two of said autoxidizable groups have the formula CH2=CR-C)(2-0 - (in the formula, R is H or CH3), (d) the material of the dispersed particles contains 0.2 to 35% by weight of the autoxidizable group; (e) said group is at least the total number of autoxidizable groups present in the material of the particles; and (f) ethylenic when the stabilizing compound is amphiphilic. Contains no unsaturations A method is provided which is characterized in that:

The present invention: - The film of the Teyoru composition dries quickly and completely when heated, and has a strong and rigid film. film, and in some cases, this film is similar to that of conventional, sterile alkyd resins. It is a surprising result that it can dry faster than film. even more amazing The fact is that these advantageous customizations can be achieved even at relatively low concentrations of said groups. This means that

The compound has the formula H2c=CR-CH2-0- (hereinafter referred to as At least two autoxidizable groups (referred to as "(meth)allylox7 groups" below) There are no limitations on the nature of this compound other than what it must contain. These groups are already Are these groups present in this compound? -j by appropriate chemical reaction which can be added to this compound. The compound itself is a monomer, i.e. Qualitatively non-polymerized and non-oligomeric, e.g. - Terumo L < Ia To'J Methylolf 0 mouths Gunno allyl ether (or the compound may be essentially an oligomer or polymer, e.g. For example, poly(allylgly/norether) may be used.

When referring to "Olycomer", the term "Olycomer" is used in the sense recognized by those skilled in the art, i.e. , "f remer compounds of molecules containing only 2, 3 or a few mers" (Federation of 5ocieties for Coating r Pgint/Coatings Dicti by sTechnology onaryJ, 1978). This compound is essentially an oligomer. It has been found that substantial benefits are obtained when the polymer is a polymer; For this reason the use of such compounds is preferred.

A compound containing 7 (meth)allylox groups of 11 or more may be present. like this Compounds such as crosslinkers, polymers formed in the same system or other f1 ) may contain a reactive group capable of reacting with the mer. If autoxidizable groups At least 20 of the total number of are (meth)allylox7 groups and such The group consists of 02 to 35 (preferably 1 to 10)% by weight of the material of the dispersed particles. If this is the case, this compound has autooxidation 7 other than (meth)allylox 7 groups. It is possible to include possible groups.

The polymer particles are different in type from both the IJ mer and the compound in the same system. It may also contain at least one polymer that does not contain (meth)allylox/groups. stomach. If the compound is essentially non-polymeric or non-olicomeric, 1 It has been found that it is preferable for the child to contain such polymers. . The polymer may be selected from a wide range of polymers known to those skilled in the art; □ is the extent to which such polymers can give the desired customization to the final dispersion. It is limited only by. Polymers can be modified or not modified. polymers, e.g. crosslinkers, compounds, other polymers or the like; It may also contain reactive groups for crosslinking by reaction with polymers within the system.

Most of the autooxidative drying ability is said to be provided by the (meth)allylox7 group. This is essential in the present invention. This concept is based on the unit equivalent of a compound. The number of units of a given autoxidizable species present in the cell as well as the number of units participating in the autoxidation reaction It is difficult to confirm because it also depends on the ability of the species. at least one other Appropriate amounts of (meth)allyl oxy/groups in a given system with autoxidizable species One way to ascertain is to remove one autoxidizable species and have all others The first step is to test the system and repeat this test for each type. Then dry Time and dryness can be checked and evaluated. Such methods are time consuming and difficult. Ru. The (meth)allylox/group is an autoxidizable group present in the material of the dispersed particles. A convenient criterion is that it must consist of at least 20 units of the number of It was discovered that

Calculation of the proportion of (meth)allylox7 groups in the total number of autoxidizable groups plays a role. It's simple. When present as a molecule or as a component of other molecules, Corrections must be made for the higher autoacidity of such polymers. do not have. The commonly understood meaning of "autoxidizable group" is a group that is subject to autoxidation. It is a molecular entity that has the ability to Therefore, in the case of drying oils or alkyd fats, Each fatty acid silver may contain up to three ethylenic double bonds, but a single It is considered to be a radically oxidizable group. However, in reality, this number Polymers with a molecular weight of 1,000,000 and an autooxidizing ability of some autoxidizable species. It cannot be applied to autoxidizable polymer species such as li(butanoene).

This difficulty is solved by converting each 300 unit of molecular weight of an autooxidizable polymer species into one autooxidizer. This can be overcome by applying the ``empirical pupil side,'' which considers it to be equivalent to a group that can be It was discovered that Therefore, autooxidation with a molecular weight of 600 Possible polymer species are considered to constitute two autoxidizable groups, with a total of 750 fractions. A molecular weight of 900 is considered to constitute two autoxidizable groups; It is considered to have a radically oxidizable group. This “Experience Summary 11” is an autoxidizable polymer such as poly(butanoene) and poly(vinyl ether). It was discovered that it works well when applied.

Monomers such that in-system polymers are formed can be used over a wide range of α, It is selected from one or more β-ethylenically unsaturated monomers. used in the present invention Typical examples of monomers that can be used include methyl, ethyl, propyl, butyl, Allyl, lauryl and stearyl acrylates and methacrylates, styrene, Vinyl chloride, vinyl acetate and methylstyrene also known as "vinyltoluene" mixed isomers and noalkyl maleate. For example, for polymers in the same system. and react with other entities such as preformed polymers, crosslinkers, or compounds such as those described above. If it is desired to provide the ability to It is also possible to use a functional fishing hook with acrylic acid and methacrylic acid. .

When the film-forming dispersed polymer particles of the present invention are formed, they are It includes polymers, compounds and, if present, other polymeric compounds.

However, these particles (are not just a simple mixture of components; they are identical During the addition polymerization reaction, which leads to the formation of small polymers within the system, the (ivy)′″ of the compound There is some degree of reaction with the 7-mer forming the same in-system polymer as the riluokif group. It is possible (and in fact often desirable). However, this In fact, it is possible to remove the ability to automatically set up the dispersion liquid to such an extent that it will never occur. That's a headline. The compounds that exist in this system exist in their original form. Although it is not possible to do so, it is considered to be within the scope of the present invention.

The selection of stable compounds is not critical to the bioactivity of the present invention; If is amphiphilic, this means that it should not contain ethylenic unsaturation. Any suitable compound may be freely selected from a variety of compounds known to those skilled in the art. It's a monkey. Stabilizing compounds containing ethylenic unsaturation have been known for a long time and are non-aqueous Although widely used for dispersion systems, relatively recently aqueous systems have been used. It is used for 11 I became angry. Examples of such stabilizing compounds are European Patent Application Publication No. 0002 Seen in issue 252. However, in the present invention, the amphiphilic base used It is necessary that the formulated compound be completely free of ethylenic unsaturation.

Stabilizing compounds suitable for use in the present invention can be selected from a variety of commercially available materials. Wear. For example, this is an amphiphilic compound without ethylenic unsaturation as mentioned above. It can be a thing. Typical examples include commercially available ionic and nonionic surfactants. . Nonionic surfactants include octyl and nonylphenol ethquinolates, e.g. For example, "Teric" (trademark) and "Triton"' (trademark) sequences. Including compounds. Ionic surfactants are cationic surfactants (e.g., various commercially available quaternary (ammonium compounds) or anionic forms (e.g. sulfated natural oils, long chain fatty acids) and various inglovirnaphthalene sulfonates, sulfoscutnates and sulfosunates. lufosufinamate).

The stabilizing compound does not necessarily have to be an amphipathic compound, and may include known suspending agents and and colloidal stabilizers. These examples (poly(vinyl aluminum) various water-soluble cellulose derivatives such as Contains complex polysaccharides such as body and tragaca; and tragaca. Stabilizing compounds are typically is present in an amount on the order of 0.1 to 20.0% by weight of the total weight of the material of the particles.

The dispersions of the present invention can be prepared by any conventional means. use One method that can be used is the preparation of a suitable polymer particle dispersion and subsequent compounding. It is the addition of things. Other methods include the preparation of bulky polymers loaded with compounds and the followed by its dispersion into water by suitable means. However, the preferred method are methods used by those skilled in the art to form multipolymer particles, i.e. That is, the polymerization of unsaturated monomers in the presence of other components. This method is convenient Is it practical, flexible, and can be carried out using a wide range of materials? This method was found to be the best method.

One preferred method for producing dispersions according to the invention is that the individual particles are compound to form a dispersion of particles, including a blend of monomers and monomers; mixing the monomer, stabilizing compound and water and then polymerizing the monomer including the step of The formation of an initial dispersion of monomer-compound particles is performed by dispersing the compound under stirring. This can be easily done by adding the monomers and monomers separately to water. but However, a preferred method is to blend the compound with monomer and This blend is then dispersed in water.

Although it is preferred that the compound and monomer be compatible, this is not essential. However, in some of the systems of the present invention, l/'i is relatively sexually compatible. stable The compound may be added to the water, or the compound and/or the monomer. It's okay. An effective variation of these methods is to add the compounds and some monomers to the water. , to start the polymerization and feed the remaining monomers into the mixture during the polymerization.

All of the above methods are similar to other,j? IJ Mama - In cases where it is desirable to add It can also be applied to

Lanocal addition polymerization can be initiated by any means known to those skilled in the art. I can do it. For example, using a lanocal initiator such as anobisinobutyronitrile, can be done. Additionally, polymerization can be easily initiated at room temperature using a redox initiation system. Can also be done. The nature of the redox initiation system used will, to some extent, depend on the polymer and model. Depends on the nature of the nomer. However, the selection of a suitable system is within the knowledge of a person skilled in the art. It is in.

Typical examples of suitable systems are L-butyl perbenzoate/sodium azcorbate and and cumene hydroxide/sodium ascorbate.

The initiation system may be an oil-bath system, in which case a mini-bulk polymerization occurs. . It is also possible to use water-soluble starter threads. The nature of the polymerization that occurs in this case is Although it is not fully understood, stabilizing compounds can be used to The compound is being formed by the monomer migrating into the formed micelles. It is thought that the particles are transferred to the polymer. However, this limits the present invention. It is not determined. The aforementioned cumene hydrofluoride/sodium ascorbate The lium system is like this because Kume/hydroberoxide is partially soluble in water. persulfates such as ammonium persulfate can be used as is preferred, and such salts are widely used in emulsion polymerization.

3. The aqueous dispersion produced by the method of the invention can be used in many applications. . For example, they can be used as film-forming components of coating compositions. can. Conventional additives such as pigments, fillers, thickeners and fungicides can be added to those skilled in the art. It can be added in an amount known to those skilled in the art.

The invention is further illustrated by the following examples. All parts in the middle part of the example are shown by weight.

The compound is an yle IJ ester that theoretically contains 8 allyloxy groups on average. So, water-based? Preparation and testing of remer dispersions. In this example, the autoxidation present l5 The only possible group is an allyloxy group, which 7.5% by weight of methyl methacrylate 25.5tt Butyl acrylate 14.5 tt Stabilizing compound 24,3 tt Azobisisobutyronitrile 0.2//B Deionized water 9.1//C Deionized water 29.7 II D Desiccant solution 3 0.7/IE 1. Allylglysitur ester with a molar ratio of 1.4:0.5:0.5, Prepared from anopic acid and inphthalic acid by polymerizing with OH/3-i to an acid value of 8~ Made of polyester resin.

2. React bisphenol A with 16 moles of propylene oxide and then react with 54 moles of propylene oxide. A nonionic stabilizer prepared by reacting with ethylene oxide.

3. Solution of copal naphthenate (8% Co metal).

Materials from A were mixed and warmed to dissolve the stabilizing compound.

Next, A was cooled to room temperature and B was added. Dissolve B and mix this mixture at high speed. In addition to C, it was diluted with D. This dispersion has a maximum particle size of 1.5 μm. Ta.

By heating this dispersion to 60°C for 4 hours and to 80°C for a further 2 hours. The polymerization was carried out with O, during which the dispersion was continuously stirred and the heat released was dissipated. E was added to this white dispersion. This formed a film at room temperature upon withdrawal. . After knee-singing for 4 hours at 25°C, the film was resistant to one volume of xylene. I discovered something.

Example 2 An aqueous polyester in which (meth)allyloxy groups comprised 25% by weight of the polymer dispersion. Preparation and testing of mer dispersions.

5.8 parts polyester, 328 parts methyl tuacrylate and 18.6 parts a The procedure of Example 1 was repeated except that butyl acrylate was used in place of the amount of Example 1. I returned it.

Polymerization was carried out as in Example 1 to obtain a white dispersion. This dispersion forms a film. accomplished. This film is xylene solvent resistant after knee-songing at 50°C for 4 hours. there were.

Example 3 An aqueous polyester in which (meth)allyloxy groups comprised 15% by weight of the polymer dispersion. Preparation and testing of mer dispersions.

34.8 parts polyester, 12.7 parts methacrylic 7 73 parts of butyl acrylate and 0.1 part of azobisinobutyronite. The procedure of Example 1 was repeated except that Ryl was used in place of the amount of Example 1.

Polymerization was carried out as in Example 1 to obtain a white dispersion. This dispersion forms a film. accomplished. The film was xylene solvent resistant after 3 hours at 25°C.

Aqueous polymer dispersion where the compound was a monomer containing on average 3 allyloxy groups Preparation and testing of fluids.

In this working example, the only autoacid group present is the allyloxy group. Riko's allyloxy/group comprised 20% by weight of the polymer dispersion.17.4 of polyester was replaced with 17.4 parts of intererythritol triallyl ether. The reactants and procedure of Example 1 were repeated except that ri was changed.

Polymerization was carried out as in Example 1, resulting in a white dispersion. This dispersion produces a film. Formed. This film can be heated for 3 hours at 50°C or for 48 hours at 25°C. After the interval, it was Kinren, and the 1IIIth hospital. Even if Example 4 Even if the allyloxy content in the sample was higher than in Example 3, at 25℃ The time required to develop solvent resistance is as follows in Example 3 where the compound is a polymer. It is more than 910 times longer than the case of .

Example 5 The compound is a monomer and the particles contain a meta(allyloxy) autobreatable group. Preparation and testing of aqueous polymer dispersions that also contain non-containing polymers.

Polyester' 12.5 A Methyl methacrylate 160 Butyl acrylate 131 Nonilfonic norethquinate stabilizing compound 3.1 Deionized water 16.8 B Deionized water 34.5C Cumene Hydroxide 0.2 D Deionized Water 22 Sodium erytholbate 01 Erythritol triallyl ether 0゜9E cobalt acetate (8% cobalt in water) Baltic) 0.6 F-broken ester composition: 1,6 hexaneol (2,5 mole fumar 2 (1, ts mol) and anopic acid (085 mol) with an acid value of 5 mg of OH/3 polyester was condensed. Add substance A to Gremi and mix at high speed. B was then added to form a fine oil-in-water emulsion and then diluted with C. Press D Remix and add to this fine emulsion to obtain polymerization of this emulsion. After polymerization, stirring E was gradually added under stirring, followed by F. Then, this dispersion was withdrawn and A film exhibiting xylene resistance was formed at 0° C. for 1 hour.

Absence of polyester or monomer pentaerythritol triallyl ether Below, no xylene resistance was achieved after 3 hours at 50°C.

Example 6 Water where the compound contains a mixture of allyloxy polyester and drying oil-modified alkyd resin Preparation and testing of polymer dispersions. The proportion of these reactants is The number of autoxidizable groups corresponded to 35% of the total number of autoxidizable groups. allyl The oxy groups comprised 3.7% by weight of the Elimer dispersion.

17.4 parts of the polyester of Example 1 was mixed with 87 parts of the same 71J ester and and 87 parts of 70% soybean oil/Staerythritol/phthalic anhydride alkyd Replaced with resin.

Polymerization was carried out as in Example 1 to obtain a white dispersion. This dispersion forms a film. ,@t,ta. This Phil'4J: Tight after knee song at 50℃ for 16 hours. It was resistant to solvents.

Example 7 Preparation and testing of dispersions using emulsion polymerization methods.

Deionized water 153.0 parts A-* Polyester 316 Methyl methacrylate 157.7 2-Ethyl hequinyl acrylate 123.9 Methacrylate 2.6 Yue ion water ioo.

Deionized water 22.4D Ammonium persulfate O, S Bira, borax 0.6 allylgrin norether/noethylene glyco in a molar ratio lO° 0.5:1.0 Reaction product of alcohol/anopic acid Grind B, add D to C, and then heat these separately at 85°C for 2 hours. It was supplied into A.

The resultant product was a white dispersion. This dispersion was prepared after knee song at 50°C for 48 hours. Afterwards, a solvent-resistant film was formed.

Claims (1)

[Claims] 1. An aqueous dispersion of a material other than a film-forming polymer, the particles of which are at least at least one compound containing two oxidizable groups and ethylenically unsaturated containing a polymer formed by addition polymerization of monomers, said dispersion further comprising a polymer formed by addition polymerization of monomers; and a dispersion comprising one stabilizing compound for said particles. Possible film-form wave i raw materials have (a) fewer groups capable of autoacidification; Both of them are of the formula, CH2=CR-CH2-0- (in the formula, R is a group consisting of H and CH3 (b) The material of the dispersed particles is 02- 35% by weight of said autoxidizable groups; (c) the group is at least the total number of autoxidizable groups present in the material of the particle; and (d) ethylene if the stabilizing compound is an ampholyte. Contains no system unsaturation A material characterized by: 2 In particles other than polymers formed from ethylenically unsaturated monomers, at least Claim 3, characterized in that one type of polymer or oligomer is present in each case. At least one compound is an olicomer or an autooxidizable film-forming compound as described in material. 4 In addition to the polymer formed from the monomers, the particles contain the autooxidizable groups. Autoxidizable according to claim 2, characterized in that it contains a polymer that does not contain film-forming material. 5. Particles are formed by polymerization of ethylenically unsaturated monomers in the presence of the above compound. The autooxidizable material according to claim 1, characterized in that it is formed by film-forming material. 6. The material of the particles contains 1 to 10 M of the autoxidizable group. Claim 1: The autooxidizable film-forming material according to claim 1. 7. The autooxidizable film-forming material according to claim 1, (a) a monomer, a compound containing at least two autolayerable groups, and water; and a stabilizing compound; (b) polymerizing the monomer to form an aqueous dispersion of particles of film-forming polymer; A method of manufacturing by a process of making it into a liquid, (c) at least two of said autoxidizable groups have the formula cu2=cR-CH2-o - (wherein R is a member selected from the group consisting of H and CH3) ri, 23 (d) the material of the dispersed particles contains 02 to 352 to 35% by weight of oxidatively kinetically oxidizable groups; (e) said group is at least the total number of autoxidizable groups present in the material of the particles; and (f) ethylenic when the stabilizing compound is amphiphilic. Contains no unsaturations A method characterized by: 8. At least one component of the mixture of monomers before polymerization is a polymer. 8. The method according to claim 7, characterized in that: 9. At least one compound is an olicomer or a polymer. 9. The method according to claim 8. 10 The mixture of monomers before polymerization contains a polymer that does not contain the autooxidizable group. 9. The method of claim 8, comprising: 11 The material of the dispersed particles contains 1 to 10% by weight of the autoxidizable group. The method according to claim 7, wherein the method is characterized by: 12. characterized in that said compound is blended with a monomer before dispersion in water 8. The method according to claim 7. 13. Claim 7, characterized in that the polymerization is initiated by an oily initiator. The method described in section. 14 Claim 7, characterized in that the polymerization is initiated by a water-soluble initiator The method described in section.