JPH01272670A - Resin composition for aqueous coating and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title composition suitable in coating, ink, etc., by neutralizing (part of) carboxyl group in a carboxyl group-containing composition obtained by copolymerizing a vinyl monomer mixture in the presence of a chlorinated polyolefin based resin and finely dispersing the neutralized copolymer. CONSTITUTION:(B) A vinyl monomer mixture consisting of (i) polyoxyalkylene ester of alpha,beta-unsaturated carboxylic acid expressed by the formula (R1 and R2 are H, phenyl or 1-4C alkyl: R3 is 1-20C alkyl; X is polyoxyalkylene chain consisting of 2-4C alkylene oxide containing ethylene oxide) and (ii) carboxyl group-containing vinyl monomer is copolymerized to provide the resin composition. Then (part of) carboxyl group in the composition is neutralized and finely dispersed and kept to >=pH 5 to provide the aimed composition.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a water-based coating resin composition and a method for producing the same, and more specifically, it can be used for paints, printing inks, adhesives, etc., and has 1 dispersion stability and water resistance. The present invention relates to an aqueous coating resin composition with excellent properties and a method for producing the same.

[Conventional technology]

Conventionally, in order to protect surfaces such as metal, concrete, paper, wood, and glass, water vapor and oxygen are allowed to pass through.
Chlorinated polyolefin resins are widely used because they are resistant to attack by various chemicals such as acids and alkalis.

Chlorinated polyolefin resins are extremely hydrophobic resins, and are generally treated with relatively low evaporation and speed, such as ketone solvents such as acetone and methyl ethyl ketone, and aromatic hydrocarbon solvents such as toluene and xylene. A solution is prepared by dissolving it in a large organic solvent or a mixture thereof, and it is applied to the metal surface by spraying or coating, and after the solvent is removed, it is baked to form a coating film. However, such a solution vehicle using an organic solvent as a medium causes the solvent to volatilize into the working atmosphere, resulting in a poor working environment.

Not only does it impair human safety, such as solvent poisoning for workers, but it also pollutes the atmosphere, and as it is a flammable solvent, there is always a risk of fire or explosion. In addition, solutions of synthetic resins in organic solvents have a high viscosity, making them difficult to apply in highly concentrated solutions, and large amounts of solvent must be used to achieve the appropriate working viscosity, requiring careful and troublesome recovery. This is extremely disadvantageous industrially.

[Problem to be solved by the invention]

As a method for avoiding such disadvantages of a solution of a chlorinated polyolefin resin in an organic solvent, a method has been proposed in which a chlorinated polyolefin resin is dispersed in water to produce a paint. However, this method requires the use of a large amount of low-molecular-weight surfactant, and as a result, the resulting paint film has significantly poor water resistance and poor dispersion stability over time. In addition, there were many problems in practical use, such as the dispersion stability being impaired by the pressure applied to the paint system during spray painting.

The problem to be solved by the present invention is to take advantage of the excellent customization of chlorinated polyolefin resins to produce metals.

When used as a coating material for concrete, paper, wood, plastic, etc., it has excellent water resistance throughout.

Another object of the present invention is to provide an aqueous coating resin composition having excellent dispersibility over time and a method for producing the same.

[Means to solve the problem]

The present invention aims to solve the above problems.

(1) In the presence of chlorinated polyolefin resin.

HC=S C-C-0-X-Rs (in the formula, R1 and R2 each may be the same or different hydrogen atom), represents a nyl group or an alkyl group having 1 to 4 carbon atoms , R5 is a hydrogen atom or has 1 carbon atom
~ 20 alkyl groups, X represents a polyoxyalkylene chain consisting of an alkylene oxide having 2 to 4 carbon atoms containing at least ethylene oxide) A resin composition obtained by copolymerizing a vinyl monomer mixture consisting of an ester and (b) a cargexyl group-containing vinyl monomer (hereinafter referred to as the resin composition used in the present invention) is dispersed in an aqueous medium. An aqueous coating resin composition (hereinafter referred to as the coating composition of the present invention) consisting of the following is provided.

The coating composition of the present invention can be produced, for example, by the following method.

That is, (1) in the presence of a chlorinated polyolefin resin,
(2) Copolymerizing a vinyl monomer mixture consisting of (a) a polyoxyalkylene ester of can β-unsaturated cargonic acid represented by general formula (1) and (a) a carboxyl group-containing vinyl monomer in the presence of a polymerization initiator. Especially with the Cargoxil Foundation? Consists of reamer and chlorinated polyolefin resin. The first step is to produce a resin composition, and after neutralizing at least a portion of the carboxyl groups contained in the resin composition with a basic compound, the neutralized product is finely dispersed in water. A manufacturing method comprising a second step in which the amount of the compound used is such that the pH of the dispersion is 5 or more.

The chlorinated polyolefin resin used in the present invention is a thermoplastic resin obtained by chlorinating chain hydrocarbon polymer substances such as polyethylene 7rideropylene, natural and synthetic dem, and in some cases rainbow maleic resin. 2 acid components
It may be contained in a proportion of not more than 7% by weight.

Commercial products of the chlorinated polyolefin resin used in the present invention and
Suit Gu-Cron 306'', [Super Chron 510
J, r Suit Darkron 602", "Sue/Darkron 773HJ, r Suit G-Cron 803LJ, "Superchron 907J, r Sue Non-Cron CR-5J, r
Examples include Superchron CR-150J.

It is possible to use a chlorinated I-lyolefin resin and a poxy resin at the same time. The epoxy resin is used for the purpose of suppressing the decomposition of the chlorinated polyolefin resin by dechlorinated water XK, and for the purpose of improving the adhesion of the coating film to the base. The number average molecular weight of the epoxy resin used for these purposes is preferably in the range of 300 to 50000.

Examples of commercially available epoxy resins used in the present invention include "Ebibu" 828J manufactured by Yuka Shell Co., Ltd.

“Epicote 1001j, rEpicote 1004J.

[Ebihut 1007J, r Ebiconi) 1009J, "
Examples include Epicote X0IOJ.

The proportion of the epoxy resin to be used is preferably in the range of 1 to 110 parts by weight per 100 parts by weight of the chlorinated polyolefin resin. A range of 50% is preferred.

α represented by general formula (I) used in the present invention. Examples of polio and sialkylene/esters of β-unsaturated carpon include (1) β-hydroxyethyl (meth)acrylate, β
- Vinyl monomer iC containing hydroxyl groups such as hydroxypropy/I/(meth)acrylate.

(4) in ethylene and glopylene oxide and/or butylene oxide (B) (4)/(B) = 100
Compound obtained by adding 1- in a random or block state at a weight ratio of 10. to 60/40: (2) Adding the above (4) and Φ) to (4)/(B) = 10
One terminal group of the polyoxyalkylene obtained by random copolymerization or block copolymerization at a weight ratio of 010 to 60/40 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the other terminal group is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. I whose terminal group is a hydroxyl group
A compound obtained by producing polyoxyalkylene glycol and esterifying it with a calgexyl-based vinyl molymer or l-mer such as acrylic acid or methacrylic acid; (3) The polyoxyalkylene glycol used in (2) above and an acrylic acid. Examples include compounds obtained by transesterification with (meth)acrylic acid esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, propyl acrylate, and decyl acrylate.

The average molecular weight of the polyoxyalkylene chain of the polyoxyalkylene ester of α,β-unsaturated cargonic acid represented by the general formula (1) used in the present invention is as follows.

A range of 1.500 to 25°OOO is preferred.

In addition, α represented by the general formula (I) used in the present invention
The content of the I-lyoxyethylene block in the polyoxyalkylene chain of the polyoxyethylene ester of β-unsaturated carginic acid is preferably in the range of 60-100% by weight, particularly in the range of 75-100% by weight. preferable. Polyoxyethylene! It is not preferable that the ROC content [i] is less than 150111 because the dispersibility of the resin composition used in the present invention in an aqueous medium tends to deteriorate.

Commercially available polyoxyalkylene esters of α,β-unsaturated carboxylic acids represented by the general formula (1) used in the present invention include 1, for example, “Flemmer PM” manufactured by NOF Corporation.
Examples include E-4000J.

Examples of cargexyl group-containing vinyl mono-i-
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
Examples include maleic acid and fumaric acid.

Other Ox-compatible vinyl mono-V- which can be used as the vinyl monomer mixture include 1, for example, styrene, vinylt/I/ene. Styrenic monomers such as 2-methylstyrene, t-butylstyrene, chlorostyrene, etc.: megyl acrylate, ethyl acrylate, isozorobyl acrylate, n-tutyl acrylate, isobutyl acrylate, n-amyl acrylate, acrylic acid Acrylic acid esters such as isoamyl, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, dodecyl acrylate: methyl methacrylate, nia methacrylate, methacrylic acid n-butyl, intutyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, hydroxyethyl nitride methacrylate, Hydroxyl group-containing monomers such as hydroxyglovir acrylate, hydroxyethyl methacrylate, and hydroxy7glopyru methacrylate: N-methylol (N-substituted (meth)acrylics such as methane acrylamide and N-cytoxymethyl (meth)acrylamide) Examples include monomers.

α represented by general formula (1) in the vinyl monomer mixture
, the proportion of polyalkylene ester of β-unsaturated cargenic acid is preferably in the range of 5 to 60% by weight, α, β-
If the proportion of the unsaturated carboxyl polyalkylene ester used is less than 5% by weight, the dispersion stability of the resin composition used in the present invention in an aqueous medium tends to deteriorate.

This is not preferable because it tends to make it difficult to emulsify the resin composition used in the present invention in an aqueous medium.

α, β-
If the proportion of the polyalkylene Nisdel of unsaturated calgenic acid used is more than 60% by weight, it is not preferred because the water resistance of the smear tends to decrease and is also economically disadvantageous.

The proportion of the cartuxyl group-containing vinyl monomer in the vinyl monomer mixture is preferably in the range of 5 to 80% by weight. The usage ratio of carboxyl group-containing vinyl monomer is 5!
If it is less than f%, the dispersion stability of the resin composition used in the present invention in an aqueous medium tends to deteriorate, which is not preferable. If the usage ratio of the carboxyl group-containing vinyl monomer is more than 80 FQB,! This is not preferred because the water resistance of the membrane tends to decrease.

The proportion of other polymerizable vinyl monomers used in the vinyl monomer mixture is preferably in the range of 0 to 90% by weight. Other polymerizable vinyl monomers are used to adjust the glass transition temperature of iK calexyl group-containing polymers and to adjust calexyl group-containing polymers.
It is used to balance the hydrophilicity and hydrophobicity of xyl group-containing polymers.

The ratio of the chlorinated polyolefin resin and epoxy resin to the vinyl monomer mixture is 40 to 60 by weight.
The range of 90:XO is preferred.

Examples of the polymerization initiator used in the copolymerization reaction of the vinyl monomer mixture include common radical polymerization initiators such as azobisisobutyronitrile and benzoyl peroxide. The proportion of these polymerization initiators used is based on the vinyl monomer mixture.

A range of 0.5 to 20% per weight is preferred.

Examples of the organic solvent used in the copolymerization reaction include:

Alcohols such as methanol, ethanol f oΔnol, butanol: Ether alcohols such as methyl cellosolve, ethyl cellosolve, fo birol, butyl cellosol, methyl calpitol, ethyl calpitol; acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl f Examples include ketones such as lopyl ketone and ethyl butyl ketone, and aromatic hydrocarbons such as toluene.

The coating composition of the present invention can be prepared by adding a base in an amount such that pi (pi) of the dispersion is 5 or more to the resin composition used in the present invention obtained by the polymerization reaction. It can be obtained by dispersing K in an aqueous medium.

The base used here is preferably ammonia or a volatile amine, and inorganic bases are not preferred because they tend to remain in the f11 film and deteriorate water resistance.

Another example of the above amine is trimethylamine.

Alkylamines such as triethylamine and butylamine: dimethylaminoethanol and jetanolamine. Alcohol amines such as aminomethylzolopanol: morpholine, etc. can be used. Ethylenecyamine, -7F
Polyvalent amines such as ethylenetriamine can also be used.

In the present invention, the aqueous medium is water alone or water containing at least 10% by weight of water. 4-! , means a mixture with a hydrophilic organic solvent. Examples of the hydrophilic organic solvent include methanol, ethanol, n-deronodanol, and inzolopanol% n-getanol.

Alkyl alcohols such as s@a-7”tanol, 1-art-getanol, inbutanol; methylcelonol f, ethylcellosolve, fa pircelonorp, butylcellonol f, hexylcellosorg, methylcarpitol,
Glycol ethers such as ethyl calpitol: Glycol ether esters such as methyl heptarosol guacetate and ethylseron luga acetate /Ila: Others, such as zolkit:S/, trimethylformamide, diaphragm alcohol, etc. Ru.

The coating composition of the present invention has extremely good dispersion stability, and when it is necessary to reduce the amount of organic bath agent contained, it is possible to use a low boiling point solvent such as acetone or methyl ethyl ketone, or tutanol. 1. A solvent that is azeotropic with water, such as 1. A coating composition containing a specific solvent with a low pressure can be obtained stably and easily by dispersing it in an aqueous medium and then distilling it under reduced pressure.

For the purpose of improving the film-forming properties of the five covering compositions of the present invention,
Plasticizers such as phthalate esters and chlorinated/4' rough-ins can also be added together with the film forming aid. Additionally, a solvent, a surfactant or an antifoaming agent may be added to the coating composition of the present invention to improve the coating properties. 5 more
It is also possible to add χ to the coating composition of the present invention using a curing agent such as a chimino resin or a phenol resin.

The characteristics of the coating composition of the present invention are as follows. The following is the general policy. Specifically, the coating composition of the present invention (1) has excellent dispersion stability compared to an aqueous dispersion obtained using a conventional emulsifier or dispersant. (2) Since no emulsifier or dispersant is used, the water resistance of the membrane is excellent. (3) Because of its excellent dispersion stability, it uses less solvent.

Can be made solvent-free.

Due to these characteristics, the coating composition of the present invention is useful as a coating material for aluminum, tin-plated copper plates, pretreated metals, steel, and the like. The coating composition of the present invention is applied to wood. It is also useful as a material for coating nonmetallic substrates such as bond fibers, plastics, ceramics, and cement substrates.

As a coating method, the conventionally known direct a-roll coating, reverse roll coating, T-coating at the anode, spray coating, and flow coating are preferable.A sufficiently cured coating film can be obtained by drying at room temperature, but 120
Preferably, a cured coating is obtained by baking conditions ranging from 5 seconds to 30 minutes at ~250°C.

The coating composition of the present invention may contain a suitable rust inhibitor,
Contains pigments, fillers, etc. 14. It can also be used in rust-preventing primers, printing inks, and anti-corrosion paints.

The present invention will be explained below with reference to five examples. In addition.

In the examples, "parts J, r'l" represent "parts by weight" and "wt%", respectively.

Example 1 (1) “Suit G-Clone 510J 75.0
(Deyu national policy) Chlorinated polyethylene manufactured by Gurde Co., Ltd.) (2) "Epicote 828 J 10゜0 parts (Ki-ki resin manufactured by Yuka Shell Co., Ltd.) (3) "Blenmar P-4000J 4.
0 parts (polyoxyalkylene ester of α, β-unsaturated carnic acid manufactured by NOF Corporation) (4) Methyl ethyl ketone xoo, o
Part (5) Methacrylic acid 8.
0 parts (6) n-butyl acrylate 4.0
Part (7) Penzoylno mother oxide 1.
0 parts (8) Tutanol 25
．． 0 parts (9) Ammonia water (28 t) 660 parts 0 tin Ion exchange water 30 (), 0 parts (1) to (4) were placed in a nitrogen-substituted 40 flask and completely dissolved, then the contents were stirred. The mixture was heated to 80 DEG C., and while maintaining the same temperature, the mixture of (5) to (7) was gradually added dropwise over a period of 2 hours, followed by further stirring at the same temperature for 3 hours. After that, (8) was added to the reaction mixture and mixed uniformly, and then a mixture of (9) and 0 () was added dropwise over 30 minutes. A coating resin composition was obtained.

The viscosity and dispersion state of this composition did not change even after the composition was left at room temperature for one week. Further, the composition after the organic compounds in this composition were distilled off under reduced pressure also showed a good dispersion state.

Example 2 and Comparative Example 1 Various aqueous coating resin compositions 1 were produced in the same manner as in the reaction system shown in Table 1 below.

In addition. The trade names or compound abbreviations shown in the table are as follows:

[Surigu-kron 306J... Deyukuni IJ,")'
Chlorinated polyglobylene "Epicote 1009J" manufactured by f company Epoxy resin MAA manufactured by Yuka Shell Co., Ltd. Methacrylic acid BA ... n-butyl acrylate St −
・Meeting...Styrene 4 obtained in each Example and Comparative Example! Evaluation of R type aqueous m fat composition by the following method:,! , and the results are shown in Table 1.

[Distributed state]

The state of water dispersion was visually evaluated. The evaluation criteria are as follows.

Q: Good dispersion.

Δ: Dispersion occurred, but two layers separated after one week.

×...poor dispersion.

[Creation of painted board for testing]

Each of the water-repellent coating resin compositions obtained in the mock and comparative examples was applied using a Jf618 par suiter onto a 1-day-thick aluminum plate, and baked for 4 minutes in a hot air oven set at 160°C. Ta. ? The near area was taken out, cooled to room temperature, and used as a painted board for testing.

1) Appearance of the paint film] Observe the condition of the paint film formed on the test coated board. 2.
It was evaluated in the following three stages.

O...Toro.

Δ...There is some turbidity.

×...opaque.

[Base grain peeling test]

100 base marks were made on the above test coating plate ((formed 711:m) by cutting lines with a safety forcepsaw blade at intervals of 1 line each in length and width.

Apply cellotape to that part using Chiban Co., Ltd.'s Seven-Off T.
After pasting the ``cellotape'', peel off the ``Cellotape''. . After peeling off the "cellotape", the aluminum column board was evaluated on the following three scales based on the number of substrate marks adhered to it.

Q-100 pieces △...70 to 99 pieces x...69 pieces or less [Water resistance test] After immersing the above test coated board in ion-exchanged water at 40°C for 240 hours, After judging according to the following criteria, two of the above-mentioned substrate peeling test needles were conducted.

[Pristar Judgment Criteria]

Q: Prista is not occurring.

Δ: Blister size according to the evaluation criteria specified in ASTM D714 8. Pristors with a density of approximately rFffJ are generated.

x: Except for the above, blister density rMEDIUMJ or higher occurs.

7, / /' 112// The7・″ // /” ' 22. / , /' [Effects of the Invention] When the aqueous coating resin composition of the present invention is used as a coating material for metal, concrete, paper, wood, plastic, etc., it provides a coating film with excellent water resistance.

It also has excellent dispersion stability over time.

Therefore, the aqueous coating resin composition of the present invention is useful for paints, printing inks, and the like.

Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. (1) In the presence of a chlorinated polyolefin resin, (
2) (a) General formula ▲ Numerical formulas, chemical formulas, tables, etc.
4 represents an alkyl group. R_3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. X represents a polyoxyalkylene chain consisting of an alkylene oxide having 2 to 4 carbon atoms and at least ethylene oxide. ) A resin composition obtained by copolymerizing a vinyl monomer mixture consisting of a polyoxyalkylene ester of an α,β-unsaturated carboxylic acid represented by (b) a carboxyl group-containing vinyl monomer is dispersed in an aqueous medium. An aqueous coating resin composition comprising: 2. The aqueous coating resin composition according to claim 1, which uses an epoxy resin together with a chlorinated polyolefin resin. 3. The average molecular weight of the polyoxyalkylene chain of the polyoxyalkylene ester of α,β-unsaturated carboxylic acid is 1,
500 to 25,000, and the content of polyoxyethylene block in the polyoxyalkylene chain is in the range of 60 to 100% by weight.
The aqueous coating resin composition according to item 1 or 2. 4. The proportion of polyoxyalkylene ester of α,β-unsaturated carboxylic acid contained in the vinyl monomer mixture is 5.
60% by weight of the aqueous coating resin composition according to claim 1 or 2. 5. The aqueous coating resin composition according to claim 1 or 2, wherein the proportion of the carboxyl group-containing monomer contained in the vinyl monomer mixture is in the range of 5 to 80% by weight. 6. Carboxyl group-containing vinyl monomer is acrylic acid,
Methacrylic acid, crotonic acid, itaconic acid, maleic acid,
The aqueous coating resin composition according to claim 1 or 2, which is selected from the group consisting of fumaric acid. 7. The aqueous coating resin composition according to claim 1, wherein the ratio of the chlorinated polyolefin resin to the vinyl monomer mixture is in the range of 40:60 to 90:10 by weight. 8. The aqueous coating resin composition according to claim 2, wherein the epoxy resin is used in a proportion of 0.1 to 110 parts by weight based on 100 parts by weight of the chlorinated polyolefin resin. 9. Chlorinated polyolefin resin and epoxy resin,
The ratio of vinyl monomer mixture used is 40:60 by weight.
The aqueous coating resin composition according to claim 2 or claim 8, which has a ratio of . 10, (1) In the presence of chlorinated polyolefin resin,
(2) (a) General formula ▲ Numerical formulas, chemical formulas, tables, etc.
R_3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. X represents a polyoxyalkylene chain consisting of an alkylene oxide having 2 to 4 carbon atoms and at least ethylene oxide. By copolymerizing a vinyl monomer mixture consisting of a polyoxyalkylene ester of an α,β-unsaturated carboxylic acid represented by The first step is to produce a resin composition made of a chlorinated polyolefin resin, and after neutralizing at least a portion of the carboxyl groups contained in the resin composition with a basic compound, the neutralized product is dissolved in water. A method for producing an aqueous resin composition for coating, comprising a second step of dispersing the basic compound in an amount such that the pH of the dispersion becomes 5 or more. 11. A method for producing an aqueous coating resin composition according to claim 10, which uses an epoxy resin together with a chlorinated polyolefin resin. 12. The average molecular weight of the polyoxyalkylene chain of the polyoxyalkylene ester of α,β-unsaturated carboxylic acid is 1
500 to 25,0000, and the content of polyoxyethylene block in the polyoxyalkylene chain is in the range of 60 to 100% by weight.
A method for producing an aqueous coating resin composition according to item 0 or item 11. 13. The aqueous coating according to claim 10 or 11, wherein the proportion of polyoxyalkylene ester of α,β-unsaturated carboxylic acid contained in the vinyl monomer mixture is in the range of 5 to 60% by weight. A method for producing a resin composition for use. 14. The method for producing an aqueous coating resin composition according to claim 10 or 11, wherein the proportion of the carboxyl group-containing monomer contained in the vinyl monomer mixture is in the range of 5 to 80% by weight. 15. Claim 1 in which the carboxyl group-containing vinyl monomer is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid.
A method for producing an aqueous coating resin composition according to item 0 or item 11. 16. The method for producing an aqueous coating resin composition according to claim 10, wherein the ratio of the chlorinated polyolefin resin to the vinyl monomer mixture is in the range of 40:60 to 90:10 by weight. 17. The method for producing an aqueous coating resin composition according to claim 11, wherein the epoxy resin is used in a proportion of 0.1 to 110 parts by weight based on 100 parts by weight of the chlorinated polyolefin resin. 18. The weight ratio of the chlorinated polyolefin resin and epoxy resin to the vinyl monomer mixture is 40:6.
The aqueous coating resin composition 19 according to claim 11 or 17 in the range of 0 to 90:10, the aqueous coating resin composition according to claim 1 or 2 A paint made of objects. 20. A printing ink comprising the aqueous coating resin composition according to claim 1 or 2.