JPH0415277A - Synthetic resin emulsion for coating and its preparation - Google Patents

Abstract

PURPOSE:To obtain the title emulsion which can form a coating film with excellent water resistance, alkali resistance and weatherability by emulsion- polymerizing a vinyl aliph. tert. carboxylate and vinyl acetate. CONSTITUTION:A vinyl aliph. tert. carboxylate of the formula (wherein R<1>, R<2> and R<3> are each a 1-6C alkyl) (e.g. a product obtained from an aliph. tert. caboxylic acid synthesized by reacting a mixture of polyolefins contg. 60wt.% or more isobutylene units with CO and water) and vinyl acetate are emulsion- copolymerized. A synthetic resin emulsion for coating which is suitable for a base of a coating which can form a coating film with excellent water resistance, alkali resistance and weatherability can be obtd. by a simple method of preparation.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a synthetic resin emulsion for paints and a method for producing the same. More specifically, the present invention relates to a synthetic resin emulsion for emulsion paints that has excellent water resistance, alkali resistance, and weather resistance, and a method for producing the same.

[Prior Art and Problems to be Solved by the Invention] Emulsion paints are paints manufactured by adding coloring pigments, pigment dispersants, plasticizers, and various other additives to a polymer emulsion obtained by emulsion polymerization. It is called a paint and does not contain organic solvents, so it is a resource-saving and pollution-free paint.
There is no danger of creating a flame.

Emulsicon paints are currently mainly used as interior and exterior paints for W-dyed products. Conventionally, polyvinyl acetate or a copolymer emulsion containing a large amount of vinyl acetate has been used as the resin for the emulsion raw material.

The problem is that these resins have low weather resistance, and for exterior applications that require weather resistance, acrylic resins, styrene-acrylic copolymer resins, or carbon 10 (hereinafter referred to as C1°) with branches at the α position are used. An emulsion of vinyl acetate resin or the like containing 30% or more of an ester component (for example, Beoha ■ manufactured by Shell Chemical Co., Ltd.), which is a synthetic fatty acid (expressed as shown below) into which a vinyl group has been introduced, is used.

However, coating films made from these resin emulsions are not always satisfactory in terms of water resistance, alkali resistance, or weather resistance.

[Step F for Solving the Problems] The present invention was made to solve the above problems, and is suitable for emulsion paints that can form coatings with excellent water resistance, alkali resistance, and weather resistance. The purpose of the present invention is to provide a synthetic resin emulsion and a method for producing the same.

That is, the first invention of the present application is based on the general formula (1) (wherein R1,
R'' and R3 represent an alkyl group having 1 to 6 carbon atoms,
11 (+, R2 and 11 (ff may be the same or different)) and vinyl acetate. The second invention of the present application is a synthetic resin emulsion for paint having the general formula (1) in the first invention.
This is a method for producing a synthetic resin emulsion for paints, which comprises emulsion copolymerizing an aliphatic tertiary carboxylic acid vinyl ester represented by ) and vinyl acetate.

Below, the method for producing a synthetic resin emulsion for paint according to the present invention and the synthetic resin emulsion for paint produced by the method will be explained in order.

The synthetic resin emulsion for paints of the present invention can be produced by emulsion copolymerization of aliphatic tertiary carboxylic acid vinyl ester represented by the general formula (1) and vinyl acetate.

The aliphatic tertiary carboxylic acid vinyl ester represented by the general formula (1) has, for example, (1) 60 isobutylene units! Step (2) of synthesizing a saturated aliphatic tertiary carboxylic acid by reacting a polyolefin mixture containing 1% or more with carbon monoxide and water in the presence of a catalyst. A process for synthesizing vinyl esters of carboxylic acids.

(v) A synthetic resin emulsion for paints can be suitably produced through the process of copolymerizing this vinyl ester with vinyl acetate.

The three steps mentioned above will be explained in order below.

(1) Step of synthesizing an aliphatic tertiary carboxylic acid.

This aliphatic tertiary carboxylic acid is produced by reacting a polyolefin mixture containing 60% by weight or more of isobutylene units, -carbon oxide, and water in the presence of a catalyst. It can be produced by the so-called Kotsuho reaction.

The polyolefin mixture may be a mixture of various polyolefins or a single polyolefin, and may also contain other substances such as paraffin that do not impede the object of the present invention.

In any case, the polyolefin mixture contains at least 60% by weight of inbutylene units, preferably from 71 to 74f!
It must contain %.

60 inbutylene units in the polyolefin mixture
If it is less than % by weight, the degree of branching of the alkyl group is small and a large amount of aliphatic tertiary carboxylic acid mixture with poor chemical stability is produced, which is not preferable.

In the present invention, the boolefin mixture contains at least 60% by weight of imbutylene units obtained by reacting a butane-phthylene fraction obtained by cracking naphtha in the presence of a Lewis acid catalyst, such as a reinforced aluminum catalyst. , preferably in a proportion of 71 to 74% by weight.

It also contains inbutylene oligomers such as diisobutylene and triisobutylene, and contains 6 inbutylene units.
Polyolefin mixtures containing at least 0% by weight are preferred.

The catalyst in the Couho reaction includes sulfuric acid, phosphoric acid,
A combination of sulfuric acid and phosphoric acid, a combination of boron trifluoride and water, a combination of boron trifluoride and phosphoric acid,
It is possible to suitably use one or more kinds selected from the group such as.

These catalysts may contain metal compounds such as cuprous oxide, silver oxide, silver sulfate, gold oxide, metallic copper, a mixture of divalent copper compounds and metallic steel, and the like.

The amount of the catalyst used may vary depending on the type of catalyst, or if a catalyst containing sulfuric acid is used, the amount of sulfuric acid used per 1 mole of C=C double bonds in the polyolefin mixture. is usually 3 moles or more.

After the completion of the Kotsuho reaction, the resulting reaction product is purified by ordinary purification operations such as distillation to obtain, for example, a carboxylic acid mixture containing a carboxylic acid having 9 carbon atoms as a main component or a carboxylic acid mixture containing a carboxylic acid mixture containing 13 carbon atoms as a main component. A carboxylic acid mixture as a component can be easily obtained.

(2) A step of synthesizing an aliphatic tertiary carboxylic acid vinyl ester.

In order to produce a vinyl ester of an aliphatic tertiary carboxylic acid such as the above general formula (1), 1. A vinylation method using catalytic vinyl group transfer, i.e. vinyl acetate, vinyl chloride, It is also possible to adopt a method of transferring a vinyl group such as vinyl ether to the aliphatic tertiary carbonic acid.

In the method α), for example, a vinyl ester is synthesized by a liquid phase reaction in the presence of a zinc salt or a mercury salt as shown in &(n).

R' (In the formula, R', R2 and R' have the same meanings as above.) In addition, the vinyl group transfer method (2) is, for example, PdC1 and alkali metal chloride, or Hg (■) A vinyl ester is synthesized by reacting an aliphatic tertiary carboxylic acid with excess vinyl acetate in the presence of a salt and sulfuric acid as shown in formula (m).

(m) (co) A process of producing a synthetic resin emulsion for paint by copolymerizing aliphatic tertiary carboxylic acid vinyl ester and vinyl acetate.

Next, the aliphatic tertiary carboxylic acid vinyl ester of general formula (1) and vinyl acetate are emulsified (co)polymerized.

The amount of 1,000 units used in emulsion copolymerization is 1 unit of vinyl acetate.
00% (mol), aliphatic tertiary carboxylic acid vinyl ester is 2 to 100%, especially 20 to 50% (molar ratio)
This is the amount that corresponds to the ratio of Use like this! Within this range, it is possible to prepare a synthetic emulsion for paints suitable for paints having coatings with excellent water resistance, alkali resistance, and weather resistance.

Therefore, if the amount of saturated aliphatic tertiary & l carboxylic acid vinyl ester used is less than 2%, it may not be possible to achieve the purpose of the present invention, and if it exceeds 100%, it may not be worth increasing the amount used. However, there are times when it may not be possible to achieve the desired effect.

In emulsion polymerization, vinyl acetate, aliphatic tertiary carboxylic acid vinyl ester, and an emulsifier are supplied in water to emulsify the raw materials, and then a polymerization initiator is added before and after adding the emulsifier for polymerization.

As polymerization initiators used, water-soluble substances that generate free radicals 1, such as potassium persulfate, sodium persulfate,
Ammonium persulfate, calcium persulfate, potassium persulfate, sodium peroxide, hydrogen peroxide, t-butyl hydroperoxide.

Examples include cumene hydroperoxide and benzoyl peroxide. Examples of retux-based catalysts include hydrogen peroxide-IS*, persulfate-acidic sodium sulfite, and cumene hydroperoxide-ferrous salt.

It is also possible to use a method in which the radiation (photo) polymerization reaction is promoted by irradiation with light such as ultraviolet rays, radiation such as α rays, β rays, γ rays, etc.

As a molecular weight regulator, for example, olefins.

Various known molecular weights that can be used for radical polymerization of vinyl compounds, etc. ! Agents can also be used.

In addition, as emulsifiers, higher fatty acids such as sodium lauryl sulfonate, higher alcohol II# ester salts, dibasic fatty acid ester salts such as dioctyl sulfosuccinate,
Anionic emulsifiers such as dodecylbenbensulfonate, polyethylene oxide alkyl ethers such as polyethylene oxide lauryl ether, polyoxyethylene lauryl esters, random or block copolymers of ethylene oxide and propylene oxide, and alkyl ethers or esters thereof. nonionic emulsifiers such as polyoxyethylene alkylphenol ethers, polyoxyethylene alkylphenol ethers, and any mixtures thereof, polyvinyl alcohol, hydroxyethylcellulose, polyN-
Water-soluble protective colloid emulsifiers such as methylolated axolamide are used.

(4) Paint base am fat emulsion 1 of the present invention! ! The synthetic resin emulsion for use as a material can be suitably produced by the step of synthesizing the aliphatic tertiary carboxylic acid vinyl ester.

The synthetic resin emulsion for paints produced usually contains 1 to 50% by mole of aliphatic tertiary carboxylic acid vinyl ester.

As long as the aliphatic tertiary carboxylic acid vinyl ester having such a number average molecular weight is an emulsion liquid that is contained in water in an emulsified state, it can be manufactured by other methods without using the above manufacturing process. I can bring it.

The synthetic resin emulsion for paints of the present invention has a stable emulsified state and is suitable as a base liquid for paints to be described later.

(5) I! Preparation of lil additive To prepare a paint using the synthetic resin emulsion for paint, a dispersant and a coloring agent are mixed with the synthetic resin emulsion for paint. Additionally, additives such as plasticizers, viscosity modifiers, light stabilizers, storage stabilizers, and fillers can be added as necessary.

Dispersants are used to uniformly disperse the emulsion copolymer and contribute to its stability.For example, polyhydric alcohols are used, and examples include ethylene glycol, propylene glycol, trimethylene glycol, phethylene gelicol, and bentanediol. , dihydric alcohols such as hexanediol, polyhydric alcohols such as glycerin 1, trimethylolethane, trimethylolpropane, and pentaerydot, polyethylene glycol with a low degree of polymerization, and polyalkyl ether of bosobrobylene guacol.

As the coloring agent, ink dyes such as ordinary dyes for water-based inks, organic pigments, 'megtI4, and mixtures thereof in arbitrary proportions can be used. most 5
Generally, organic pigments and inorganic pigments for printing inks are preferably used.

Examples of the inorganic pigments include zinc oxide calcium carbonate, barium sulfate, zinc white, lithopone, titanium dioxide, titanium white, chromium yellow, cadmium yellow, nickel titanium yellow, red iron oxide, mica-like iron oxide, lead white, red lead, Silver vermilion, ultramarine (milory blue, Prussian blue), deep blue (ultramarine), cobalt oxide, titanium dioxide-coated mica, strontium chromate, titanium yellow titanium black, synchromate, iron black, molybdenum red, molybdenum white, molybdenum orange, litharge, Emerald green, Guinea green, cobalt blue, mercury cadmium sulfide, ultramarine, mineral fast yellow 1
Cadmopon, navel yellow (antimony, yellow iron oxide, chromium dizinc yellow, carbon black, lead sulfate, lead molybdate, cadmium carbonate, lead sulfide, zinc sulfide, cadmium sulfide, mercury sulfide, etc.) Ru.

As the organic pigment, an azo pigment, a phthalocyanine pigment, etc. can be used. Specifically, for example, Banza Yellow, Benzidine Yellow, Permanent Yellow, Palcan First Yellow, Suren Yellow, Permanentret, Benzidine Yellow, etc. Dane Orange, Palkan Orange, Pig Orange 17, Threnpril Orange, Ballalet, Permanent Carmine, Bar 7 Nent Bordeaux, Brill First Scarlet, Piglet 23, Palkan Fire Red, Pyrazolone Red, Watching Red, Resolelet, Lake Red , Helio Red, Lake Bordeaux, Bon Maroon Dark, Toluidine Red, Quinacridone Red, Chromophthalento, Big Violet 23, Dioxazine Violet, Dokuto Soa Pure Blue Zeki, Victoria Blue Lake, Big Blue 15, Big Blue 16,
Big Blue 17, Diamond Green Lake, Copper Phthalocyanine Green, Steel Phthalocyanine Blue, Big Green B, Green Gault Diamond Black, etc. may be mentioned.

In the present invention, the paint can be prepared by mixing each of the components in the synthetic resin emulsion for paint and dissolving or dispersing each component.

[Example] Next, the present invention will be specifically described using examples and comparative examples.

First, the synthesis of aliphatic tertiary carboxylic acid, which is a raw material for the emulsion of the present invention, will be described as a reference example.

(Reference example) 270 g of a strong acid mixture consisting of (1) sulfuric acid 64% by weight, phosphoric acid 29% by weight and 7% water and 6.4 g of cuprous oxide.
and 11 in an electromagnetic stirring type stainless steel autoclave, and after sufficiently replacing the inside of the autoclave with carbon monoxide gas, the temperature was set to 25°C, and the carbon oxide gas pressure was set to 1.
Maintained at 5kg/c■2, 1,000r over 3 hours
pm to completely dissolve the cuprous oxide.

Subsequently, while maintaining the temperature and pressure at the above values, 33.6 g of diisobutylene (0.3 morsine) was fed into the autoclave over 90 minutes. The composition of the diisobutylene used was 2.4.4- The content was 70.91% by weight of trimethyl-1-pentene, 222.1% by weight of 2.4-4-1-trimethyl-2-pentene, and 7.0% by weight of other carbon atoms having 8 carbon atoms.

The carbon monoxide consumed in the reaction is - carbon oxide pressure or 15 kg
/cm'' was replenished into the autoclave.

After stopping the supply of diisobutylene, stirring was continued for another hour at mmt. In this case, the acid strength of the catalyst was -8.1 before the reaction, and changed to -7.5 after the reaction. was.

After the reaction was completed, the resulting reaction mixture was diluted 3 times, and the extraction was repeated 3 times with 2 DOm fl of n-hexane.

After distilling off the n-hexane, the crude carboxylic acid mixture shown in Table 1 47. Ig was obtained.

This crude carboxylic acid mixture was subjected to vacuum distillation, and the
28.0 g of a fraction at 1"C/1 smHg was obtained.

In the manner described above, a carboxylic acid mixture containing C9 aliphatic tertiary carboxylic acid as a main component was obtained.

(2) Diisobutylene: Instead of using 13.6g, C
11-olefin 0.8% by weight, Cl2-olefin 9
4.: li amount% and C13-olefin 4.9% by weight
52. The poly-t reflex mixture having a composition consisting of:
The same procedure as in the above reference example was carried out except that 4 g was used and the reaction temperature was kept at 5°C. A crude carboxylic acid mixture having the composition shown in Table 1 was obtained.

In this case, the acid strength of the catalyst was -8.1 before the reaction, gradually decreased during the reaction, and changed to -7.6 after the reaction.

This crude carboxylic acid mixture was subjected to vacuum distillation, and as described above, a carboxylic acid mixture containing C1) aliphatic tertiary carboxylic acid as a main component was obtained.

(A) of the carbon vinyl ester, the carboxylic acid mixture containing the C9 aliphatic tertiary carboxylic acid as a main component synthesized in (1) of (a) above and excess vinyl acetate are mixed with mercuric acetate and sulfuric acid. was reacted in the presence of , to synthesize an aliphatic tertiary carboxylic acid vinyl ester as shown in formula (m).

At this time, the catalyst system caused a transfer reaction of the vinyl group, but no cleavage reaction between the carbon atom of the vinyl group of vinyl acetate and the oxygen atom of the carboxyl group occurred.

(B) A vinyl ester was synthesized in the same manner as in (b) and (1) above from the carboxylic acid mixture containing CI3 aliphatic tertiary carboxylic acid as a main component synthesized in (2) of (a) above.

Next, an example will be described about the production of an emulsion by copolymerization of the aliphatic tertiary carboxylic acid vinyl ester obtained in Reference Example and vinyl acetate.

(Example 1) 5 with stirrer, thermometer, -flow condenser and dropping funnel
In a 00ml round bottom flask, add polyethylene oxide lauryl ether (manufactured by Dai-Kogyo Seiyaku) as an emulsifier.
75 g of water containing 6.0 g was added. Next, 100 g of vinyl acetate, which had been mixed in advance, was added to (1) of Reference Example (b).
15 g of the 50 g of vinyl ester of the carboxylic acid mixture containing C, an aliphatic tertiary carboxylic acid as the main component obtained in step ) was added.

After purging the reaction system with nitrogen, the internal temperature was raised to 50°C without stirring.
rose to When the internal temperature rose to 50° C., 10 ml of an aqueous solution containing 0.45 g of potassium persulfate and 10 ml of an aqueous solution containing 0.45 g of sodium sulfite were added. After the polymerization had begun, 35 g of the vinyl ester of the carboxylic acid mixture based on the aliphatic tertiary carboxylic acid described above was added via the dropping funnel over a period of 2 hours. Further, the polymerization initiator was added in portions.

After the addition was completed, the internal temperature was maintained at 50° C. for 1 hour to complete the copolymerization, and the mixture was cooled to prepare a copolymer emulsion.

(Example 2) 50 g of the mixture containing the CI3 aliphatic tertiary calphone vinyl ester component obtained in (2) of Reference Example (b) was copolymerized and emulsified with vinyl acetate in the same manner as in Example 1. A liquid was prepared.

(Comparative Example 1) As the monomers to be added dropwise in Example 1, a mixture of 100 g of vinyl acetate and 50 g of Beoha 10 (vinyl ester made from C + O saturated aliphatic carboxylic acid, manufactured by Shell Chemical Co., Ltd.) was used. Emulsion copolymerization was carried out in the same manner as in Example 1 except that a copolymer emulsion was prepared.

(Comparative Example 2) An emulsion was prepared by polymerizing in the same manner as in Example 1, except that 150 g of vinyl acetate was used as the monomer to be added one drop in Example 1.

A paint was prepared for the performance test of the paint, and the performance was examined using the zero-order method to prepare 1 nit of white paint.

■ Preparation of pigment paste Titanium dioxide (rutile type) 200 parts Calcium carbonate 250 Sodium hexametaphosphate 0.82% methylcellulose aqueous solution 100 Water
80 Total 630.8 The above formulation was mixed uniformly to form a pigment paste.

■ Preparation of paint samples Emulsions 3 prepared in Examples 1 to 2 and Comparative Examples 1 to 2 above
00 parts were mixed with 630 parts of the above pigment paste and 10 parts of ethylene glycol, and kneaded until uniform, to prepare four types of paint samples.

■ Test method for paints Each of the paint samples obtained as described above was applied with a brush to a flexible board to form a paint film. Coating film test The emulsions obtained in the above Examples and Comparative Examples were tested in the following manner.

The results are shown in Table 142.

Test method water resistance Alkali resistance Compliant with JIS-561i3.

Applying paint to flexible board Then, add 3XNa OH aqueous solution to the room. After warming and soaking for 48 hours, the condition of the coating film I observed the situation.

accelerated weather resistance Colorfastness: Compliant with JIS-5663.

Chalk resistance Compliant with JIS-5663.

However, the evaluation is done on a five-point scale, and the higher the score, the better.

[Effect of Application] According to the present invention, a synthetic resin emulsion for paints suitable as a base material for paints that can form a paint film with excellent water resistance, alkalinity, and weather resistance, and a simple method for producing the same are provided. can be provided.

Patent applicant: Idemitsu Petrochemical Co., Ltd. l'4

Claims (4)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1, R^2 and R^3 represent an alkyl group having 1 to 6 carbon atoms, and R^1 , R^2 and R^3 may be the same or different from each other. Synthetic resin emulsion for paint. (2) The paint according to claim 1, characterized in that the aliphatic tertiary carboxylic acid vinyl ester represented by the general formula (I) according to claim 1 and vinyl acetate are emulsion copolymerized. A method for producing a synthetic resin emulsion. (3) The coating material according to claim 2, wherein the aliphatic tertiary carboxylic acid vinyl ester represented by the general formula (I) is used in an emulsion copolymerization using a molar ratio of 2 to 100% with respect to vinyl acetate. A method for producing a synthetic resin emulsion. (4) Aliphatic tertiary carboxylic acid vinyl ester represented by general formula (I) contains 60% by weight of isobutylene units.
The synthetic resin emulsion for paints according to claim 2, which is synthesized using an aliphatic tertiary carboxylic acid synthesized by reacting a polyolefin mixture containing the above ratio with carbon monoxide and water as a raw material. Method of manufacturing liquid.