JPH06509383A - water-based coating composition - 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] water-based coating composition The present invention provides a primer and a primer for improving the adhesion of coated materials to polyolefin substrates. The present invention relates to compositions useful as such. The compositions of the invention do not contain significant amounts of organic solvents. Main departure The present invention also relates to methods of preparing these compositions.

Polyolefins, such as polypropylene, thermoplastic olefins and polyethylene The application of paints and other coatings to the substrate of the It is typically difficult because it is chemically inert.

This problem can be solved by using two separate methods using adhesion promoting compositions. It has already been overcome. One method is to separate the polyolefin substrate and the paint. using an adhesion promoting composition as a primer application. Primer The coating adheres well to both the polyolefin and the paint, thereby forming a one-piece triad. A component structure is formed and the paint becomes the outer part of the structure. polyolefin Another method for application is to use an adhesion promoting composition as an additive with the paint. It is that you are. This technique is known in the art as “stir in )” It is sometimes referred to as the use of adhesion promoters.

A number of polymeric materials are available as possible components for such adhesion promoters. has been investigated. Chlorinated polyolefins are a prime choice because of their price and performance. - has been found to be extremely satisfactory as a polymer component for compositions. . See, for example, U.S. Pat. Nos. 966, 947, 4.962.149 and 4.954.573 are As a polymeric component of adhesion promoting compositions useful for coating lyolefin substrates. discloses chlorinated polyolefins which are highly satisfactory.

Chlorinated polyolefins have been used to prepare highly satisfactory adhesion promoting compositions. However, chlorinated polyolefins require large amounts of organic solvents, such as xylene or had to be combined with toluene. The use of large amounts of organic solvents is undesirable. stomach. Unless complicated solvent recovery methods are used, primer coating compositions can be applied using organic solvents. into the atmosphere, resulting in pollution problems and primer coating compositions. This is because both health problems for the applicator will be caused.

We have developed a highly satisfactory water-based solution which preferably does not contain large amounts of organic solvents. We have discovered a coating composition.

Primer for polyolefins, consisting of chlorinated polyolefins, water and other materials - Compositions reported to be useful as coatings are disclosed in International Publication No. WO 901. It is disclosed in No. 2056.

The plastic for polyolefins consists of two types of polymers, water and other materials. A composition reported to be useful as an immersion application is disclosed in British Patent No. 22724. It is disclosed in No. 18.

The composition of the present invention is (A) a chlorinated polyolefin having a specific range of molecular weight, softening point, and chlorine content; (B) a carboxylic acid functional resin, and (C) Water can be considered as a ternary composition comprising:

Optionally, amines, surfactants and organic solvents may be present in the composition.

Chlorinated polyolefins useful in the present invention range from 9.000 to 150.000. Based on molecular weight, softening point ranging from 75 to 115°C and weight of polyolefin Broadly described as chlorinated polyolefins with chlorine content ranging from 15 to 35% by weight can do. One embodiment of the chlorinated polyolefin useful in the present invention is Disclosed in U.S. Pat. No. 3,579,485. In another embodiment of the invention Chlorinated polyolefins useful as chlorinated polyolefins are disclosed in U.S. Pat. The chlorinated polyolefin reacts with the hydroxy group-containing primary amine to cause chlorination and ionic acid. This is a midized polyolefin. These polyolefins are Known in the art and described in U.S. Pat. No. 4.954.573 . Therefore, the chlorinated, non-ionized Midized polyolefins are also available as salts as described in U.S. Pat. No. 4,954,573. The use of either hydrogenated or imidized polyolefins is within the scope of the present invention. term" By "chlorinated polyolefin" is meant both of the polymers mentioned above.One implementation of the invention In embodiments, the chlorinated polyolefin has between 100.000 and 150.000 Molecular weight in the range, softening point in the range 80-115°C and weight of the chlorinated polyolefin. Contains chlorinated polyolefins having a chlorine content ranging from 20 to 35% based on the amount can become. In another embodiment of the invention, the chlorinated polyolefin is , molecular weight in the range of 110.000 to 130.000, range of 95 to 105 °C Chlorine in the range of 25-35% based on the softening point of and the weight of the chlorinated polyolefin The composition may comprise a chlorinated polyolefin that increases the amount of chlorinated polyolefin. Preferred embodiment In the chlorinated polyolefin, the molecular weight ranges from 9.000 to 16.000. , 18-22 based on the softening point and polyolefin weight in the range of 80-95°C. It has a chlorine content in the range of %. In the present invention, the molecular weight of the chlorinated polyolefin is It is the number average molecular weight.

In the present invention, the amount of chlorinated polyolefin in the composition is in the range of 70 to 30% by weight, preferably based on the total amount of carbon and carboxylic acid functional resin. preferably in the range of 70 to 40% by weight, more preferably in the range of 70 to 45% by weight. .

The carboxylic acid functional resins useful in this invention can be mixed with chlorinated polyolefins. The molecular weight is high enough to produce a polyolefin, and it can be combined with a chlorinated polyolefin. In the sense of preparing the primer tube cloth composition of the present invention, chlorinated polyol is used. Contains polymers with carboxylic acid functionality such that they are sufficiently miscible with the olefins. can become.

According to one theory, carboxylic acid functional resins have two functions. The first is this The resin acts as a medium and the chlorinated polyolefin has liquid homogeneity in the medium. 1I11! can do. Second, the carboxylic acid functional group of the resin is neutralized, providing a mechanism for preparing a mixture of the two polymers and water. Ru. Therefore, an important property of resins is that they are useful for preparing liquid homogeneous mixtures. The resin must have sufficient miscibility with the chlorinated polyolefin, and the resin must have a sufficient amount of chlorinated polyolefin. It has an acid functional group that allows it to be dispersed through neutralization.

Preferably, the carboxylic acid functional resin is an alkyd resin, a polyester resin or an acrylate resin. It is rill resin. More preferably, the carboxylic acid functional resin is an alkyd resin or an alkyl resin. It is a cryl resin.

Alkyd resins useful in the present invention are well known in the art and include polyhydric alcohols. and a polyfunctional acid in which part of the acid component may be long chain fatty acids of vegetable oil. It is a product of the stellation reaction. Examples of polyfunctional acids include phthalic anhydride, adipic acid, maleic anhydride, isophthalic acid, cepatic acid, azelaic acid, terephthalate Rulic acid, trimellitic anhydride, linoleic acid, riluic acid, benzoic acid, hexahydride Phthalic anhydride, tetrahydrophthalic anhydride, 1. 4-cyclohexanedi Carboxylic acid or fumaric acid may be mentioned. An example of a polyhydric alcohol is glycerol. trimethylolethane, trimethylolpropane, diethylene glycol, Neopentyl glycol, 1.4-cyclohebosandimethator, 2. 2.　 4-1-limethyl-1,3-bentanediol, 1,6-hexanediol, l, 2-propylene glycol, 1,2-propanediol, ethylene glycol, Butylene glycol, dipropylene glycol and pentaerythritol are listed. It will be done. A group of oils containing mustard oil and tall oil used to modify alkyd resins. obtained from The amount of oil modification in the resin that is effective for the present invention is within the range of <4596 (short 1 (short oil alkyd) or within the range of 45-65% (medi um) oil alkyd).

The alkyd resins useful in the present invention have a number in the range of 300 to 30,000 g per mole. It can have an average molecular weight and an acid number greater than 20. More preferably, a The acid value of the rukido resin should be within the range of 25-150.

More preferably, the alkyd resin has a non-volatile content of 70%, ranging from Z to Z2. medium chain oil alkyds with a Gardner viscosity of and an acid number ranging from 50 to 59. It is.

Acrylic resins useful in the present invention are well known in the art, and there are many acrylic resins useful in the present invention. A reaction product of acrylic acid and methacrylic acid and acrylic acid monomers derived from esters. It is an addition polymer. Examples of acids and esters that can be used include: Acrylic acid, methacrylic acid, styrene, methyl methacrylate, ethyl acrylate butyl acrylate, methyl acrylate, ethyl methacrylate, butyl acrylate, butyl acrylate, ethyl methacrylate, methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl Methacrylate, butyl acrylate, propyl methacrylate, lauryl meth acrylate, 2-hydroxypropyl methacrylate, 2-ethylhexyl methacrylate Acrylate, hexyl methacrylate, cyclohexyl methacrylate, Nitoki siethylua, acrylate, ethylhexyl acrylate, cyclohexyl acrylate rate, hexyl acrylate, butadiene, vinyltoluene, vinylpyrrolidine and 2-hydroxypropyl acrylate.

The acrylic resin useful in the present invention ranges from 400 to 40.000 g per mole. and an acid number greater than 20. More preferably acrylic resin has an acid value ranging from 25 to 150.

In a preferred embodiment, the acrylic resin has an acid number in the range of 220-250, 10 Ring and ball softening point in the range of 0 to 120°C and number average molecular weight in the range of 2000 to 3000 It is a solid acrylic oligomer that grows in volume.

Polyester resins useful in the present invention are well known in the art and include polyfunctional Condensation polymers, which are polyesterification products of carboxylic acids and polyfunctional alcohols It is. Examples of polyfunctional carboxylic acids include phthalic anhydride, isophthalic acid, and lohexanedicarboxylic acid, adipic acid, azelaic acid, maleic anhydride, sepa Chic acid, terephthalic acid, trimellitic anhydride, linoleic acid, lilunic acid, benzoic acid Acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, fumaric acid, l , 4-cyclohexanedicarboxylic acid and succinic acid. polyfunctional alco Examples of alcohols include ethylene glycol, neopentyl glycol, and diethylene glycol. Recall, 1,6-hexanediol, cyclohexane dimetatool, glycero trimethylolethane, trimethylolpropane, butylene glycol, 1.4-Cyclohexane dimetatool, 1.2-propylene glycol, 1.2 -propanediol, dipropylene glycol, pentaerythritol and 2. 2.4-) dimethyl-1,3-bentanediol.

Polyesters useful in this invention range from 100 to 10.000 g per mole. It has a number average molecular weight of Useful polyester resins have acid numbers greater than 20. It is something to do. A more preferred polyester resin has an acid value in the range of 25 to 150. It is something that you have.

The amount of carboxylic acid functional resin is the amount of chlorinated polyolefin and carboxylic acid functional resin. in the range of 30 to 70% by weight, preferably in the range of 30 to 60%, based on the total weight of More preferably, it is in the range of 30 to 55% by weight.

By combining certain chlorinated polyolefins and certain carboxylic acid functional resins This results in particularly preferred embodiments of the invention. For example, preferred chlorinated polio If the refin is a non-imidized material, the non-volatile content of 70%, Z-22 said medium chain oil having a Cardnet viscosity in the range of and an acid number in the range of 50 to 59. The use of ralkyls represents a particularly preferred embodiment of the invention. Furthermore, preferred If the chlorinated polyolefin is an imidized material, the acid value ranges from 220 to 250, 1 Ring and ball softening point in the range 00-120°C and number average in the range 2000-3000 Particularly preferred according to the invention is the use of solid acrylic oligomers as described above having a molecular weight of This is a new implementation.

The composition of the present invention contains water. The amount of water depends on a number of factors, e.g. May vary widely depending on needs, transportation efficiency and specific customer needs. Main departure An important characteristic of brightening compositions is that these compositions have a high resistance to light to which the composition is applied as a coating. Can be made using less water than would typically be needed; may be added by the customer when preparing the subsequent coating composition. It is. This may depend on the particular temperature, pressure or time used to prepare the diluted composition. Simply adding additional water into the composition prepared by the manufacturer without taking into account the This can be done by injection.

Manufacturers therefore prepare “concentrated” products with low water content and provide customers with additional quantities. release concentrated products to customers without the need to incur additional costs by shipping can be loaded. “Concentrated” products also avoid over-dilution of the paint This is desirable when the adhesion promoter composition is to be used as an additive to paints. There are many.

The amount of water can vary widely, and there is no upper limit on the amount of water, but at least four components Water must be present in the composition to prepare the mixture. There is a lower limit on the amount. Exact amount of water needed to prepare the required mixture can vary, but generally prepares mixtures with injectable viscosity properties. There must be at least 40% water by weight in the composition, based on the total weight of the composition, in order to Must.

The composition of the present invention may optionally contain an amine. Amines are aromatic or fatty Although it may be aliphatic, aliphatic amines are preferred. In a preferred embodiment, fat The aliphatic amine may be a primary, secondary or tertiary amine, optionally with other amines. of oxygen-containing functional groups. Amines useful in the present invention are generally The molecular weight ranges from 20 to 200.

A particularly preferred group of amines are primary, secondary and tertiary aliphatic amines, generally the following: It has 1 to 3 functional groups that can be represented by the general formula below: ■ R, -NR, or In the above formula, R1=RT is independently Hl or a straight chain having 1 to 20 carbon atoms or is a branched alkyl, hydroxyalkyl or alkoxyalkyl group; R 1-R7 is further a substituted alkyl group, i.e., one or more carbons in the radical ether, hydroxy or mercapto moieties, e.g. (nopropyl) amine, or by adding another functional group to its It can also include the above substitutions.

Another group of particularly preferred amines within said class include R1-R in the formula Is 7 specifically substituted with one or more hydroxyl (-OH) functional groups? or containing primary, secondary or tertiary aliphatic amines.

Another group of preferred amines can be represented by the following formula: R,R.

R1-(NHri, or R,-(Nl(), or R-(Rlo N R++) In the above formula, n is l or 2, and R* + Rs + R+o and R1+ are independent straight-chain or branched alkyl or hydroxyalkyl having 1 to 20 carbon atoms; or alkoxyalkyl group. These chains can be substituted with other functional groups as described above. may be replaced.

Yet another group of amines preferred for the practice of this invention includes one or more ethers. a first having from 1 to 3 amine functional groups that also contain ole bonds or alkoxy bonds; Secondary and tertiary aliphatic amines. Such materials include poly(oxyalkylene)dia Sometimes called Min. Particularly preferred are ethoxylated or propoxylated materials.

Preferred exemplary amines for use in the present invention include: 2-Aminoethanethiol: 2-aminoheptane; 2-amino-1-hexanol: 6-amino-1-hexanol; Allylamine: 2-amino-3-methyl-1-butanol; 2-amino-2-methyl-1,3- Propanediol; 2-amino-2-methyl-1-propatool: 2-amino- 1-Pentanol: 5-amino-1-pentanol; 3-amino-1-propertool: Ammonium hydroxide; N,N'-bis(2-aminoethyl)-1,3-propanediamine; N,N'-bis(3-aminopropyl)-1,3-propanediamine: 1.3-bis(dimethylamino)-2-propanol: 1-(N,N-bis( 2-hydroxyethyl)aminoco-2-propatool; N, N'-bis(2-hydro5-ethyl)ethylenediamine: Decylamine: ■, 4-diaminobutane; t,io-diaminodecane: 1,3-diamino-2-hydroxypropane; 3,3'-diamino-N-methyl Dipropylamine: 1,2-diamino-2-methylpropane: 3-(dibutylamine) mino)propylamine; 5-diethylamino-2-pentanol; 3-(diethylamino) l-diethylamino-2-propanediol; l-diethylamino-2-propanediol 3-diethylamino-1-propanol; 3-diethylaminoprobylamine hmm; Diethylenetriamine: N,N-diethylethanolamine; N,N-diethylethylenediamine; N, N-diethylmethylamine: N, N'-diethyl-1,3-propanediamine: diisobutylamine; Diisobubanolamine: Diisobuviramine: 2-(diisopropylamino)ethanol: 3-diisopropylamino-1,2 -Propanediol; N,N-diisopropylethylamine; l-dimethylamine No-2-propertool; 2-dimethylaminoethanol: 3-dimethylamino-1-propanol; 3-dimethylaminopropylamine: 1, 3-dimethylbutylamine; 3.3-dimethylbutylamine: N,N-dimethylethanolamine; N,N-dimethylethylamine; N,N-dimethylethylenediamine: N, N-dimethyl-N'-ditylethylenediamine; N, N'-dimethyl- 1,6-hexanediamine; 2,5-dimethyl-2,5-hexanediamine; 1 , 5-dimethylhexylamine; 2.2-dimethyl-1,3-propanediamine; (±)-1,2-dimethylpropane Pyramine; dipropylamine; 3-ethoxypropylamine; Ethylamine: 2-(ethylamino)ethanol; N-ethylbutylamine: 2-ethylbutylamine; N-ethyljetanolamine; Ethylenediamine; Hexamethylene diamine; N-isopropylethylenediamine: N'-isopropyl-2-methyl-1,2-propanediamine; N, N, N ’, N’-Tetramethyl-1,4-butanediamine: N, N, N’, N'-tetramethyldiaminomethane; N, N, N', N'-tetrame Tylethylenediamine: N, N, N', N'-tetramethyl-1,6- Hexanediamine: N, N, N', N'-tetramethyl-1,3-pro Panjiamine 2N, N, 2. 2-tetramethyl-1,3-propanediamine Nitriisooctylamine; Triisoprobianolamine; 2-(methylamino)ethanol; N-methylbutylamine: 1-methylbutylamine; 2-methylbutylamine; N-methyljetanolamine; N-methylethylenediamine; N-methyl-1,3-propanediamine; terioctylamine: Propylamine; 2-(propylamino)ethanol: 1-tetradecylamine: and Tris(3-aminopropyl)amine.

Mixtures of the aforementioned materials can also be used.

Preferred amines are ammonium hydroxide, dimethylethanolamine, triethyl Ruamine, jetanolamine, ethanolamine, dimethylamine, diethyl Amines, piperazine, morpholine and 2-amino-2-methyl-1-propazine It is le. A particularly preferred option is when the carboxylic acid functional resin is an alkyd resin. Min is ammonium hydroxide. If the carboxylic acid functional resin is acrylic, A preferred amine is dimethylethanolamine.

The amount of amine is based on the total amount of chlorinated polyolefin and carboxylic acid functional resin. The amount is in the range of 0 to 20% by weight, preferably 10 to 20% by weight.

Surfactants useful in the present invention include nonionic and cationic surfactants. This includes both agents. By the term "non-ionic surfactant" refers to a surfactant that does not contain any functional groups. By the term “cationic surfactant” A field that ionizes in water to produce large positively charged ions and small negatively charged ions. means surfactant.

In the present invention, the nonionic surfactant has a molecular weight of up to 500 or more. and can include polymeric materials.

As nonionic surfactants, they contain various polar groups, which can cause some parts of the molecule to Name a material in which one part of the molecule is hydrophilic and the other part of the molecule is hydrophobic. I can do it. Examples of such materials include polyethyleneoxypolyol and Ethoxylated alkylphenols may be mentioned. Particularly preferred nonionic surfactants As agents, alkylphenoxypoly(ethyleneoxy)alcohol, primary ethyl alcohol, etc. Examples include silicated alcohols and secondary ethoxylated alcohols. Preferably, non- The ionic surfactant is an alkyl phenoxy poly(ethyl chloride) having 22 to 215 carbon atoms. (renoxy) alcohol.

Cationic surfactants useful in the present invention have molecular weights ranging from 100 to 1000. and can be broadly described as alkoxylated amines. Preferably, The thionic surfactant is an alkoxylated aliphatic amine or an alkoxylated taloa. It's Min.

The amount of surfactant is based on the total weight of chlorinated polyolefin and carboxylic acid functional resin. It ranges from 1 to 30% by weight based on.

Materials typically used in the industry, such as fillers, wetting agents and flow aids, pigments, resins, etc. It can contain fats and solvents.

The composition of the present invention can contain an organic solvent as long as the amount of organic solvent is not large. death Accordingly, the compositions of the present invention preferably contain less than 50%, based on the weight of the composition; Preferably it contains less than 25% organic solvent.

The compositions of the invention can be used as adhesion promoting compositions in two different ways. can. The preferred method depends on many factors, e.g. the particular substrate to be applied, the nature and degree of other materials used in the paint formulation, and The choice depends on other factors. According to one method, the coating composition of the invention preferably Preferably, the prepared composition is diluted with water, the desired additives are added, and then the diluted composition is The polyolefin substrate is subjected to conventional means such as spraying, brushing or dipping. It can be applied as a separate primer application.

The composition of the present invention is applied as a coating, and after drying the coating, paint is applied to the plastic. Apply over the immersion coating.

The primer application adheres to both the polyolefin and the paint, thereby providing a uniform forming a three-component structure of the body with paint on the outer part of the structure Ru. According to another method, the composition of the invention may be so-called "stir-in". Can be used as a paint additive. In this method, the composition is added to The resulting mixture is applied to a polyolefin substrate to Form a single application that adheres to the fin substrate.

The compositions of the present invention have suitably small particle sizes to make the mixture useful during application. It is a mixture with Therefore, as for the composition of the present invention, an expert calls it "emulsion" ``and'' as well as ``dispersions'', as well as all other mixtures of various components. Physical forms are also included. For example, some experts say that water-containing mixtures Mixtures with particle sizes in the range of 0.1-10 microns are specified as "emulsions". other Experts recommend water-containing mixtures with particle sizes greater than 10 microns. Considered a “dispersion”. Although both of these types of mixtures are within the scope of this invention, , the invention is not limited to these or any other types of specific mixtures, and the particle size However, any physical form may be used as long as the mixture is small enough to be used for application. including mixtures of possible types.

The composition of the present invention can be used to improve adhesion of paint to polyolefin substrates. Although particularly useful as accelerators, the compositions of the present invention may also be used as paints in their own right. , which not only protects the substrate but also becomes decorative as a result of the addition of pigments. It is also within the scope of this invention to form a final protective coating.

The compositions of the invention are prepared by a novel method consisting of two steps.

The first is to prepare a mixture of chlorinated polyolefin and carboxylic acid-functional resin, and then A mixture consisting of a mixture of lyolefin and resin and water is prepared.

Chlorinated polyolefins and carboxylic acid functional resins are prepared as a mixture of polymeric materials. The mixture is prepared by methods well known in the art. salt When both the hydrogenated polyolefin and the carboxylic acid functional resin are in solid form, These are mixed in a twin-screw extruder or made into powder, and then the mixed powder is Can be extruded using a screw extruder. Additionally, hot roll mills, e.g. Mixture by combining resin and chlorinated polyolefin in hot three-roll mill can be prepared. Cool this mixture and then powder before adding other ingredients. It can be pulverized into fine powder.

If the chlorinated polyolefin is a solid and the carboxylic acid functional resin is a liquid or solution, , heating the mixture above the softening point of the chlorinated polyolefin and then heating the mixture above the softening point of the chlorinated polyolefin. Fins and resin can be mixed together. Chlorinated polyolefins are high shear It can be mixed with the resin by applying mixing.

water and optionally a mixture of amines and surfactants and chlorinated polyolefins and a mixture of carboxylic acid functional resins to prepare a mixture of polyester and water. It can be prepared by methods well known in the art. One way If the material is The mixture is prepared by applying high shear to the . According to another method, the chlorinated pot The heated mixture of lyolefin and carboxylic acid functional resin is stirred as is well known in the art. Combine with heated mixture of water and amine using stirring technique.

In the following examples, the compositions of the invention contain chlorinated polyolefins, carboxylic acid functional Prepared from resin, water and optionally amine, surfactant and organic solvent. how many In some examples chlorinated polyolefins and carboxylic acid functional resins are stirred materials. and into a container equipped with means to do so. Start stirring and then pour the contents of the container. It was heated to a constant temperature for a certain period of time. Other examples include chlorinated polyolefins and carboxylic acids The functional resins were combined into a mixture using a standard three-piece mill. water and optionally The amine, surfactant and organic solvent are then added and then stirred at high shear. A mixture was prepared. Storage stability testing of selected compositions for 2-8 weeks at 25°C The test was carried out using a visual inspection test using a lath container after one week. Paint adhesion testing of selected compositions Tests were conducted according to ASTM D 3359-83, Method. paint adhesion test The composition is made of polypropylene and polyolefin modified with elastomeric polymers. This was done by applying These materials are commonly referred to commercially as “thermoplastic olefins.” It is named in the industry and abbreviated as "TPO". The composition is applied by spraying and then Dry at room temperature. Using a commercially available automotive paint system, then 2 minutes for 30 minutes. Baking was done at 50°F.

Example 1 This example includes specific chlorinated polyolefins, specific carboxylic acid functional resins, water and alcohol. This figure specifically shows the preparation of the composition of the present invention using Min.

Molecular weight in the range 9,000-16,000, softening point in the range 80-95°C and Chlorinated, non-chlorinated to develop a chlorine content ranging from 18 to 22% based on the weight of the polyolefin. 50 g of imidized polyolefin: and medium chain oil having an acid value in the range of 50 to 59. Carboxylic acid salts that are medium ail alkyd resins (70% solids) A mixture consisting of 50 g of functional resin was prepared. The mixture was heated at 105°C for 2 hours. . 10 g of ammonium hydroxide (28%) and 200 g of water were then added and for 10 minutes A mixture was obtained by subjecting to high shear stirring.

The resulting composition was diluted with sufficient additional water to form a typical commercially used A primer coating composition was obtained and a paint adhesion test was conducted with the following results.

Polypropylene 100% adhesive TPO 100% adhesive Example 2 This example demonstrates the use of different amounts of the same materials used in Example 1. This figure specifically shows the preparation of the composition of the invention.

A mixture consisting of 30 g of polyolefin and 70 g of alkyd resin was prepared. this The mixture was heated at 121° C. for 1 hour. 8g ammonium hydroxide (28%) and water 150 g was then added and the mixture was obtained by subjecting it to high shear stirring for 10 minutes. Ta. A stability test was conducted at 25°C for 8 weeks, but a slight amount of sediment was observed. this Dilute the composition with sufficient additional water to add a typical primer used commercially. -When we obtained the coating composition and conducted a paint adhesion test, we obtained the following results. .

Polypropylene 100% adhesive TPO 100% adhesive Example 3 This example demonstrates the preparation of the composition of the invention by using a different amine than that used in Example 1. The preparation is specifically shown.

A mixture consisting of 50 g of polyolefin and 50 g of alkyd resin was prepared. this The mixture was heated for 2 hours at +21"C. 4 g dimethylethanolamine and 2 g water 00 g was then added and the mixture was obtained by subjecting it to high shear stirring for 10 min. Ta. As a result of a stability test conducted at 25° C. for 8 weeks, there was no change at all. This composition Typical primer applications used commercially by diluting with sufficient additional water A composition was obtained and a paint adhesion test was conducted to obtain the following results.

Polypropylene 100% adhesive TPO 100% adhesive Example 4 This example demonstrates the use of different amounts of the same materials used in Example 3. This figure specifically shows the preparation of the composition of the invention.

A mixture consisting of 70 g of polyolefin and 30 g of alkyd resin was prepared. this The mixture was heated at 121°C for 12 hours. 2g dimethylethanolamine and water 200 g was then added and subjected to high shear stirring for 10 minutes to obtain a mixture. 2 A stability test was conducted at 5°C for 8 weeks, and a slight precipitate was observed. This composition Typical primer coatings used commercially can be diluted with enough additional water to A fabric composition was obtained and a paint adhesion test was conducted with the following results: Polypropylene l009ft adhesive TPO 100% adhesive Example 5 This example demonstrates the use of different amounts of the same materials used in Example 1. This figure specifically shows the preparation of the composition of the invention.

A mixture consisting of 25 g of polyolefin and 25 g of alkyd resin was prepared. this The mixture was heated at 121°C for 2 hours. Ammonium hydroxide (28%) 10g and A mixture was then obtained by adding 100 g of water and subjecting it to high shear stirring for 10 minutes.

A stability test was conducted at 25° C. for 6 weeks, and a slight precipitate was observed. This composition Typical primer coatings used commercially can be diluted with enough additional water to A fabric composition was obtained and a paint adhesion test was conducted with the following results: Polypropylene 100% adhesive TPO 100% adhesive Example 6 This example demonstrates the use of different amounts of the same materials used in Example 5. This figure specifically shows the preparation of the composition of the invention.

A mixture consisting of 35 g of polyolefin and 15 g of alkyd resin was prepared. this The mixture was heated at 117,121° C. for 2 hours. Ammonium hydroxide (28%) 5g and 100 g of water was then added and the mixture was obtained by subjecting it to high shear stirring for 10 minutes. . A stability test at 25°C for 6 weeks resulted in a large amount of precipitate. This composition Add a typical commercially used primer by diluting it with sufficient additional water. -A coating composition was obtained and a paint adhesion test was conducted with the following results: 20% adhesiveness TPO 100% adhesive Example 7 This example demonstrates the use of different amounts of the same materials used in Example 5. This figure specifically shows the preparation of the composition of the invention.

A mixture consisting of 25 g of polyolefin and 25 g of alkyd resin was prepared. this The mixture was heated at 121"C for 2 hours.Ammonium hydroxide (28'IM,) 1 g and 100 g of water were then added and the mixture was mixed by subjecting it to high shear agitation for 10 minutes. I got it. A stability test at 25°C for 6 weeks resulted in a large amount of precipitate. this The composition is diluted with sufficient additional water to A limer coating composition was obtained and a paint adhesion test was performed with the following results: Lopylene 0% adhesiveness TPO40% adhesiveness Qi-1 This example uses a different carboxylic acid functional resin than that used in Example 7. This figure specifically shows the preparation of the composition of the present invention.

50g polyolefin and chain-terminating alkyd resin with acid value 35 (70% solids)5 A mixture consisting of 0 g was prepared. Heat this mixture for 1o min at 121"C. Ta. 8 g of ammonium hydroxide (28%) and 100 g of water are then added and stirred with high shear. A mixture was obtained by stirring for 10 minutes. Stability test conducted at 25°C for 8 weeks However, a large amount of precipitation occurred. Diluting the composition with sufficient additional water to Typical primer coating compositions used commercially were obtained and paint adhesion tests were conducted. We conducted an experiment and obtained the following results: Polypropylene 100% adhesive TPO 100% adhesive Example - "1" This example uses a different carboxylic acid functional resin than that used in Example 8. 1Ill+ of the composition of the present invention will be specifically shown.

From 30g of polyolefin and 70g of acrylic resin (solid content 65%) with an acid value of 9o A mixture was prepared. This mixture was heated at 121° C. for 2 hours. Ammonium hydroxide 6 g of Ni(2896) and 100 g of water were then added and subjected to high shear stirring for 10 minutes. A mixture was obtained. Diluting the composition with sufficient additional water to Typical primer coating compositions used commercially were obtained and paint adhesion tests were conducted. We conducted an experiment and obtained the following results: Polypropylene 100% adhesive TPO 100% adhesive Example IO This example includes chlorinated polyolefin, carboxylic acid functional resin, amine, surfactant and This figure specifically shows the preparation of the composition of the present invention using water and water.

Prepare a mixture consisting of 50 g of polyolefin and 50 g of alkyd resin with an acid value of 85. did. This mixture was heated at 121"C for 2 hours. Dimethylethanolamine 4 g, nonylphenoxy poly(ethylene oxide) having an HBL value in the range of 13-14. C) Next add alcohol tg and 200 g of water and subject to high shear stirring for 10 minutes. A mixture was obtained. When a stability test was conducted at 25°C for 2 weeks, a large amount of precipitate was formed. It was. This composition is diluted with sufficient additional water to be used commercially. A typical primer coating composition was obtained and a paint adhesion test was conducted with the following results. Obtained: Polypropylene 100% adhesive TPO 100% adhesive Example 11 This example was prepared in Example 10 except with a different carboxylic acid functional resin. This figure specifically shows the preparation of the composition of the present invention similar to the above.

A mixture consisting of 50g of polyolefin and acrylic resin with an acid value of 90 (solid content 60%). A compound was prepared. This mixture was heated at 121"c for 2 hours.

4g dimethylethanolamine, alkylphenoxypoly(ethyleneoxy)a 2 g alcohol and 200 g water were then added and subjected to high shear stirring for 10 minutes. A mixture was obtained. A two week stability test at 25°C showed no changes at all. won. Dilute this composition with sufficient additional water to A typical primer coating composition was obtained, and a paint adhesion test was conducted with the following results. Obtained polypropylene 100% adhesive TPO 100% adhesive Example 12 This example was prepared in Example 1O except that a different carboxylic acid functional resin was used. This figure specifically shows the preparation of the composition of the present invention similar to the above.

50g of polyolefin and 50g of acrylic resin (solid content 70%) with an acid value of 45 A mixture was prepared by subjecting it to shear. 4g dimethylethanolamine, 2 g of alkylphenoxy poly(ethyleneoxy) alcohol and 200 g of water. A mixture was then obtained by adding and subjecting to high shear stirring for 10 minutes. at 25°C A two week stability test resulted in a large amount of precipitate. Add enough of this composition A typical primer coating composition that is used commercially can be diluted with water. Then, a paint adhesion test was conducted and the following results were obtained.

Polypropylene 20% adhesive TPOtoo%adhesion Example 13 This example consists of a chlorinated polyolefin, a carboxylic acid functional resin, an amine and water. This figure specifically shows the preparation of the composition of the present invention.

50g of polyolefin and 50g of acrylic resin (solid content 80%) with an acid value of 35 A mixture was prepared by subjecting it to shear. 4g of dimethylethanolamine and 200 g of water was then added and the mixture was obtained by subjecting it to high shear stirring for 10 minutes. Ta. A stability test for 2 weeks at 25°C resulted in a large amount of precipitate. This composition Add a typical commercially used primer by diluting it with sufficient additional water. -A coating composition was obtained, and a paint adhesion test was conducted to obtain the following results.

Polypropylene 20% adhesive TPO 100% adhesive Example 14 This example was prepared in Example 12 except that a different carboxylic acid functional resin was used. This figure specifically shows the preparation of the composition of the present invention similar to the above.

50 g of polyolefin and 50 g of alkyd resin (solid content 80%) with an acid value of 34 were A mixture was prepared by subjecting it to shear. 4g dimethylethanolamine, Add 4 g of alkylphenoxypoly(ethyleneoxy) alcohol and 250 g of water to the following A mixture was obtained by adding to the solution and subjecting it to high shear stirring for 10 minutes. 2 at 25°C When a weekly stability test was carried out, a large amount of precipitate was formed. Add enough water to this composition to obtain a typical commercially used primer coating composition. Then, a paint adhesion test was conducted and the following results were obtained.

Polypropylene 0% adhesive TPO 100% adhesive Example 15 This example was prepared in Example 14 except that a different carboxylic acid functional resin was used. This figure specifically shows the preparation of the composition of the present invention similar to the above.

50 g of polyolefin and saturated polyester resin with acid value 68 (solid content 75%)5 A mixture was prepared by subjecting 0 g to high shear. dimethylethanolamide 4 g 1 alkylphenoxy poly(ethyleneoxy) alcohol 2 g and water 20 0g was then added and the mixture was obtained by subjecting it to high shear stirring for 10 minutes. 25 Stability testing at °C for 2 weeks resulted in reversible phase separation.

Example 16 This example was prepared in Example 15 except that a different carboxylic acid functional resin was used. This figure specifically shows the preparation of the composition of the present invention similar to the above.

50 g of polyolefin and a saturated polyester resin with an acid value in the range of 24 to 34 A mixture was prepared by subjecting 50 g of 85% solids in silane to high shear. . 4g dimethylethanolamine, alkylphenoxypoly(ethyleneoxy) 2 g alcohol and 200 g water are then added and subjected to high shear stirring for 10 minutes. A mixture was obtained. A two-week stability test at 25°C showed reversible phase separation. occurred.

Example 17 This example includes chlorinated polyolefin, carboxylic acid functional resin, amine, surfactant, This figure specifically shows the preparation of the composition of the present invention consisting of an organic solvent and water.

50 g of polyolefin and acrylic modified polyester with acid number ranging from 58 to 66 A mixture was prepared by subjecting 50 g of resin (50% solids) to high shear.

4g dimethylethanolamine, alkylphenoxypoly(ethyleneoxy)a 4 g of alcohol, 4 g of xylene and 200 g of water were then added and high shear stirring was carried out for 10 min. A mixture was obtained by intermixing. A two-week stability test at 25°C showed that A precipitate was formed.

This composition is diluted with sufficient additional water to form a typical commercially used A primer coating composition was obtained, and a paint adhesion test was conducted to obtain the following results.

Polypropylene 100% adhesive TPO 100% adhesive Example 18 This example was prepared in Example 16 except with a different carboxylic acid functional resin. The aa of the composition of the present invention similar to the above is specifically shown below.

50 g of polyolefin and acid value acrylic resin (70% solids) are subjected to high shear. A mixture was prepared by: 4g of dimethylethanolamine, alkylphene 2 g of oxypoly(ethyleneoxy) alcohol and 200 g of water are then added and the A mixture was obtained by subjecting it to shear agitation for 10 minutes. Stability test for 2 weeks at 25℃ When this was done, a large amount of precipitate formed. Dilute this composition with sufficient additional water A typical commercially used primer coating composition was obtained and used for paint contact. An adhesion test was conducted and the following results were obtained: Polypropylene 90% adhesion TPO 100% adhesive Example 19 This example includes chlorinated polyolefin, carboxylic acid functional resin, amine, surfactant, This figure specifically shows the preparation of the composition of the present invention consisting of an organic solvent and water.

Molecular weight in the range of 9,000-16,000, softening point and point in the range of 80-95°C. Imidized chlorine with a chlorine content ranging from 18 to 22% based on the weight of the lyolefin 13g of polyolefin and 13g of solid-phase acrylic resin with an acid value of 230 were rolled into three rolls. A mixture was prepared by combining in a bottle. This mixture is cooled and then ground. The granules were heated at 121'C for 1 hour. Ammonium hydroxide 1 5g, HL818.6 nonionic nonylphenoxy(ethyleneoxy)al 1 g of coal, 10 g of xylene and 150 g of water were then added and high shear stirring was continued for 20 minutes. A mixture was obtained by intermixing. Dilute this composition with sufficient additional water A typical commercially used primer coating composition was obtained and used for paint contact. An adhesion test was conducted and the following results were obtained; Polypropylene 100% adhesion TPO 100% adhesive Example 20 This example includes chlorinated polyolefin, carboxylic acid functional resin, amine, organic solvent and This figure specifically shows the preparation of the composition of the present invention consisting of water.

Molecular weight in the range of 100,000-150,000, softening in the range of 80-115°C Chlorine with an amount of chlorine ranging from 20 to 35% based on the point and weight of the polyolefin 50 g of polyolefin, an alkyd resin with an acid value in the range of 50 to 59 (solid content 70 %) and 50 g of xylene are combined at 66°C. A mixture was prepared by: 10g dimethylethanolamine and 250g water was then added and subjected to high shear stirring for 10 minutes to obtain a mixture. at 25℃ A 3-week stability test revealed that a slight precipitate was present. Add enough water to this composition to obtain a typical commercially used primer coating composition. We conducted a paint adhesion test and obtained the following results: Polypropylene 0% adhesion TPO70% adhesiveness Example 21 This example includes chlorinated polyolefin, carboxylic acid functional resin, amine, organic solvent and This figure specifically shows the preparation of the composition of the present invention consisting of water.

Molecular weight in the range 110,000-130,000, softening in the range 95-105°C Chlorine with a chlorine content ranging from 25 to 30% based on point and polyolefin weight 50 g of polyolefin, an alkyd resin with an acid value in the range of 50 to 59 (solid content 70 %) and 50 g of xylene are combined at 66°C. A mixture was prepared by: 10g dimethylethanolamine and 250g water was then added and subjected to high shear stirring for 10 minutes to obtain a mixture. 25°C When a three-week stability test was conducted, no change occurred. Add sufficient supplement to this composition. Typical primer application compositions used commercially by diluting with additional water. The product was obtained and a paint adhesion test was performed with the following results: Polypropylene 0% Adhesiveness TPO 100% adhesive International search report orb/IICQ21nG2R6 international search report Continuation of the front page.

(51) Int, C1,5 identification symbol Internal office reference number C08L 67108L PL 8933-4JCO9D123/28 PFA 7107-4J1331 00 PGF 7921-4J167102 PKX 8933-4JPLA 8933-4J 167108 P L J 8933-4 JI

Claims (1)

[Claims] 1. (A) Molecular weight in the range of 9,000 to 150,000, in the range of 75 to 115°C The amount of chlorine ranges from 15 to 35% by weight based on the softening point of the polyolefin and the weight of the polyolefin. based on the total weight of component (A) and component (B). 70 to 30% by weight of component (A) and (B) carboxylic acid functional resin. 30-70% by weight based on the total weight of minutes (B); (C) a primary, secondary or tertiary amine having a molecular weight in the range of 20 to 200; 0 to 20% by weight based on the total weight of (A) and component (B), and (D) Water A composition comprising. 2. The chlorinated polyolefin has a molecular weight in the range of 9,000 to 16,000. , a softening point in the range of 80-95°C and an amount of chlorine in the range of 18-22%. 1. The composition according to item 1. 3. The chlorinated polyolefin has a molecular weight in the range of 9,000 to 16,000. , chlorination with a softening point in the range of 80-95°C and a chlorine content in the range of 18-22% The composition according to claim 1, which is an imidized polyolefin. 4. The above carboxylic acid functional resins include alkyd resins, polyester resins and acrylic resins. The composition according to claim 1, wherein the composition is selected from the group consisting of resins. 5. The alkyl resin has a non-volatile content of 70% and Gar in the range Z to Z2. medium chain oil with a dner viscosity and an acid number in the range 50-59 5. The composition according to claim 4, which is an alkyd. 6. The acrylic resin has an acid value of 220-250 and a temperature range of 100-120°C. A solid phase acrylic having a ring and ball softening point and a number average molecular weight in the range of 2000 to 3000. 5. The composition according to claim 4, which is a polyoligomer. 7. If the above amines are ammonium hydroxide, dimethylethanolamine, or Thylamine, diethanolamine, ethanolamine, dimethylamine, diethylamine Ruamine, piperazine, morpholine and 2-amino-2-methyl-1-propano The composition according to claim 1, wherein the composition is selected from the group consisting of: 8. The composition further comprises: (E) surfactant from 1 to 30% based on the total weight of component (A) and component (B); weight%, The composition according to claim 1, comprising: 9. The surfactant may be an alkylphenoxy poly(ethyleneoxy)alcohol. from the group consisting of primary ethoxylated alcohols and secondary ethoxylated alcohols. 9. The composition of claim 8, wherein the composition is a selected nonionic surfactant. 10. The surfactant may be an alkoxylated fatty amine or an alkoxylated tallow. The composition according to claim 8, which is a cationic surfactant selected from the group consisting of amines. thing. 11. the amount of component (A) is in the range 70-40% by weight, and the amount of component (B) 3. A composition according to claim 1, wherein the amount is in the range of 30 to 60% by weight. 12. (A) Molecular weight in the range of 9,000 to 16,000, temperature in the range of 80 to 95°C Having a chlorine content ranging from 18 to 22% based on softening point and polyolefin weight Add chlorinated, non-imidized polyolefin to the total weight of component (A) and component (B). 70-45% by weight based on (B) 70% non-volatile content, ranging from Z to Z2 A medium chain oil alkyd with a Gardner viscosity and an acid number ranging from 50 to 59. , 30-55% by weight based on the total weight of component (A) and component (B), (C) water 10 to 2 ammonium oxide based on the total weight of component (A) and component (B) 0% by weight, and (D) water A composition comprising. 13. (A) Molecular weight in the range of 9,000 to 16,000, temperature in the range of 80 to 95°C Having a chlorine content ranging from 18 to 22% based on softening point and polyolefin weight Chlorinated, imidized polyolefin based on the total weight of component (A) and component (B) 70-45% by weight, (B) acid value of 220-250, range of 100-120°C. A solid phase atom having a ring and ball softening point of Based on the total weight of component (A) and component (B), the crylic oligomer is 5% by weight, (C) Dimethylethanolamine based on the total weight of component (A) and component (B). 10 to 20% by weight, and (D) water A composition comprising. 14. A polyolefin product coated with the composition of claim 1. 15. (A) (1) Molecular weight in the range of 9,000 to 250,000, 75 to 115 softening point in the range of °C and in the range of 15-35% by weight based on the weight of the polyolefin. A chlorinated polyolefin having a chlorine amount of 70-30% by weight, and (2) carboxylic acid functional resin, based on component ( A mixture comprising 30 to 70% by weight based on the total weight of 1) and component (2). and then (B) (1) the mixture prepared in step (A), (2) 20-200 A primary, secondary or tertiary amine having a molecular weight in the range of is prepared in step (A) 0 to 20% by weight based on the weight of the mixture, and (3) Water A method comprising preparing a mixture comprising: 16. The chlorinated polyolefin has a molecular weight ranging from 9,000 to 16,000. Claims having a softening point in the range of 80-95°C and an amount of chlorine in the range of 18-22% The method according to item 14. 17. The chlorinated polyolefin has a molecular weight ranging from 9,000 to 16,000. chlorine with a softening point in the range of 80-95°C and an amount of chlorine in the range of 18-22% 15. The method according to claim 14, wherein the imidized polyolefin is an imidized polyolefin. 18. The carboxylic acid functional resins mentioned above are alkyd resins, polyester resins and acrylate resins. 15. The method of claim 14, wherein the resin is selected from the group consisting of rill resins. 19. The alkyl resin has a non-volatile content of 70% and a Ga in the range Z to Z2. rdner viscosity and an acid number ranging from 50 to 59. 18. The method according to claim 17. 20. The acrylic resin has an acid value in the range of 220 to 250 and a temperature of 100 to 120°C. hardness having a ring and ball softening point in the range of and a number average molecular weight in the range of 2000 to 3000. 18. The method of claim 17, wherein the acrylic oligomer is a phase acrylic oligomer. 21. The above amines may be ammonium hydroxide, dimethylethanolamine, or Ethylamine, diethanolamine, ethanolamine, dimethylamine, diethylamine Thylamine, piperazine, morpholine and 2-amino-2-methyl-1-propyl 15. The method according to claim 14, wherein the compound is selected from the group consisting of nols. 22. The mixture prepared in step (B) further contains (4) a surfactant in step (A). 1-30% by weight based on the total weight of the prepared mixture 15. The method according to claim 14, comprising: 23. The surfactant is alkylphenoxypoly(ethyleneoxy)alco a group consisting of alcohols, primary ethoxylated alcohols and secondary ethoxylated alcohols; 22. The method according to claim 21, wherein the nonionic surfactant is selected from: 24. The surfactant may be an alkoxylated fatty amine or an alkoxylated tallow. The method according to claim 21, which is a cationic surfactant selected from the group consisting of amines. Law. 25. The amount of component (1) in step (A) is in the range of 70 to 40% by weight, and The method according to claim 14, wherein the amount of component (2) in step (A) is in the range of 30 to 60% by weight. Law. 26. (A) (1) Molecular weight in the range of 9,000-16,000, 80-95°C Softening point in the range, and chlorine in the range of 18-22% based on the weight of the polyolefin chlorinated imidized polyolefin ▽ having an amount of 70-45% by weight based on weighed weight, and (2) 70% non-volatile content, Z~ medium chain oil having a Gardner viscosity in the range of Z2 and an acid number in the range of 50 to 59; 30 to 55 weight of lualkyd based on the total weight of component (1) and component (2). % and then (B) (1) Mixture prepared in step (A), (2) ammonium hydroxide in step 10-20% by weight based on the weight of the mixture prepared in (A), and (3) water A method comprising preparing a mixture comprising: 27. (A) (1) Molecular weight in the range of 9,000-16,000, 80-95°C Softening point in the range, and chlorine in the range of 18-22% based on the weight of the polyolefin The total amount of chlorinated imidized polyolefin of component (1) and component (2) 70-45% by weight, and (2) an acid number of 220-250, 100-45% by weight; A ring and ball softening point in the range of 120°C and a number average molecular weight in the range of 2000-3000. Based on the total weight of component (1) and component (2), a mixture comprising 30-55% by weight of (B) (1) The mixture prepared in step (A), (2) dimethylethanolamine , 10-20% by weight based on the weight of the mixture prepared in step (A), and (3) Water A method comprising preparing a mixture comprising: