JPS5889638A - Pigment composition - Google Patents

Abstract

PURPOSE:To obtain titled composition capable of forming films of high extensibility and free from any crack, by incorporating a pigment in a vinyl ester or its copolymer aqueous dispersion containing, as a protective colloid, a specific polyvinyl alcohol-based copolymer. CONSTITUTION:The objective composition comprising (I) a pigment and (II) a vinyl ester or its copolymer aqueous dispersion containing, as a protective colloid, a polyvinyl alcohol-based copolymer prepared by the saponification, in an alcohol solution, of a copolymer comprising, as essential components, (A) a monomer selected from >=6C fatty acid vinyl esters, >=6C alkylvinyl ethers and >=6C alpha-olefins, (B) an ethylenic unsaturated carboxylic acid or its lower alkyl ester or its acid anhydride, and (C) vinyl acetate. The component (A) is preferably a branched fatty acid vinyl ester with its carboxyl group attached to the alpha- site to the tertiary or quaternary carbon atom.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a stable RI composition consisting of a vinyl ester or vinyl ester copolymer aqueous dispersion containing a polyvinyl alcohol (hereinafter referred to as PVA) copolymer as a protective colloid and a noble pigment. In more detail, it relates to (a) O fat-resistant vinyl esters with 6 or more carbon atoms, alkyl vinyl ethers with 6 or more carbon atoms, and 6 or more carbon atoms.
At least one monomer selected from the group consisting of the above a-olefins; It is obtained by emulsion polymerization or emulsion co-polymerization of a vinyl ester using a PVA-based copolymer obtained by acetylating a copolymer containing the three essential components of ester in an alcohol solution as a protective colloid. Mixtures of aqueous dispersions and pigments relate to compositions that have excellent properties in forming crack-free films with high elongation.

Aqueous dispersions of vinyl esters or polyesters containing PVA as a protective colloid generally have good pigment dispersibility, and mixtures with pigments are widely used for coatings, paper processing, etc. However, due to the increase in the cost of resins in recent years, studies have been made to see if the conventional performance can be obtained by mixing with as little aqueous dispersion as possible. The present inventors focused on the miscibility of polyvinyl alcohol, which is a protective colloid, and studied the miscibility of an aqueous dispersion thereof with a pigment, and as a result, the present invention was accomplished. In other words, we attempted to solve the problem by modifying and improving the PVA of Hosan colloid, and found that when using a PV-based complex in which hydrophobic groups and ionic groups were introduced at the same time, it became difficult to mix with pigments. - It has been found that the film of the material mixture is uniform, the apparent elongation is increased, and there are no cracks. (as a hydrophobic group with respect to the PVA) fatty acid vinyl ester having 6 or more carbon atoms,
Higher alkyl vinyl ethers with 6 or more carbon atoms and a-olefins with 6 or more carbon atoms, 0 ethylenically unsaturated carboxylic acids or lower alkyl esters or acid anhydrides thereof as ionic groups, and 0) vinyl acetate as main constituents. When carrying out emulsion polymerization or co-synthesis of vinyl esters using a PVA-based copolymer obtained by saponifying a copolymer containing these three components as essential components in an alcohol solution as a protective colloid, The present invention was completed based on the discovery that it is possible to produce an emulsion that meets the objectives of the present invention.

As a component of the PVA copolymer used in the present invention, a monomer having a so-called large aliphatic hydrocarbon group having 6 or more carbon atoms is selected, and a so-called small aliphatic hydrocarbon group having 5 or less carbon atoms. Monomers having this effect do not exhibit this effect. Examples of fatty acid vinyl esters having 6 or more carbon atoms used as a component in the present invention include vinyl laurate and vinyl stearate. ester.

2.2. If the carboxyl group is tertiary or quaternary, such as t4 tetramethylparerianic acid vinyl ester or a mixture of saturated branched fatty acid vinyl esters having an average carbon number of 10, etc.
Preference is given to branched fatty acid vinyl esters which are present in the α-position relative to the carbon atom.

Examples of alkyl vinyl ethers having 6 or more carbon atoms include lauryl vinyl ether, dodecyl vinyl ether,
Octadecyl vinyl ether etc. can be applied. Furthermore, examples of α-olefins having 6 or more carbon atoms include heptene-1, octene-1°dodecene-1, octadecene-1
can be applied.

(Examples of ethylenically unsaturated carboxylic acids or lower alkyl esters thereof or acid anhydrides used as homogeneous components include acrylic acid, methacrylic acid, croton i!, maleic acid, itaconic acid, citraconic acid, aconitic acid and its methyl, Lower alkyl esters such as c-methyl, acid anhydrides, etc. are used, but dicarboxylic acids such as itaconic acid, maleic acid, and citraconic acid, and lower alkyl esters thereof such as methyl and ethyl thereof, and acid anhydrides are used. Among these, maleic anhydride*, maleic acid monomethyl ester, and itaconic acid can be preferably used.

(2), (2), and (2) used in the present invention.
The blending ratio of component (A) contained in the copolymer with component G) as an essential component varies depending on the number of carbon atoms, but is 40.8 to 7' mol within 0.2 to 10 mol%. % ranges are even more preferred. The blending ratio of component (c) contained in the copolymer varies depending on the blending ratio of component (b), but is 0.2 to 10.0 mol%, especially 0.5 to 7.
A range of 0 mol% is preferred.

The PVA-based copolymer used in the present invention is produced by known polymerization and saponification methods. ), @ and (q components are respectively added in bulk or continuously, and no f8m motor is used.
is combined with a known radical polymerization catalyst such as 2,21-azobisisobutyronitrile or benzoyl peroxide in the presence of a lower alcohol such as methyl alcohol or ethyl alcohol. The copolymer obtained by the polymerization reaction is dissolved in alcohol and, if necessary, hydrous alcohol, and saponified.

As the alcohol, lower alcohols such as methyl alcohol and ethyl alcohol are particularly suitable. These (D
y L: I-Ls ji 40 m19/7) If it is less than 1, it is atenthone, #sapon methyl ester, acetic acid ethyl ester.

As the saponification catalyst, known catalysts such as alkali or acid catalysts can be used, which may contain a solvent such as benzene.

There are no particular restrictions on the degree of saponification of the PV-based co-summer, but it may be completely saponified or partially saponified as long as the XfB properties are substantially maintained. .

The PVA copolymer obtained above is used alone as a colloid to emulsion copolymerize vinyl ester and the like in the presence of a catalyst in an aqueous phase by a known method.

A good emulsion is obtained.

In this invention, the use of an emulsifier in combination is not an essential condition, but there is no problem in using other emulsifiers in combination as an auxiliary means, for example, for adjusting the particle size. In addition, as a protective colloid, the purpose can be sufficiently achieved by using the PV-based water-bathable synthetic resin alone; however, in some cases, other protective colloids such as ordinary unmodified PVA, polyacrylic acid, or polymethacrylic acid may be used. Acids and their salts, polyvinyl alkyl ethers, co-compounds of vinyl acetate and acrylic acid or methacrylic acid, or vinyl acetate-maleic anhydride co-compounds, saponified products thereof, lower alkyl vinyl ether-maleic anhydride co-compounds cellulose derivatives such as alkyl cellulose, hydroxyalkyl cellulose, alkyl hydroxyalkyl cellulose, carboxymethyl cellulose, alkyl starch, carboxymethyl starch,
Oxidized starch, gum arabic, gum tragacanth, polyalkylene gellicols, etc. may be used during polymerization or optionally added after polymerization to impart the desired properties to the emulsion; Auxiliary agents used during emulsion polymerization, such as liquid regulators, monohydric or polyhydric alcohols, lubricants, antifoaming agents, etc., may be used together during or after the polymerization.

When other emulsifiers and/or protective colloids are not used in combination, the yam-based copolymer is used in an amount of about 1 to 40% by weight, preferably 2 to 10'M%, based on the monomers.

The present invention is characterized in that the aqueous dispersion of vinyl ester or copolymer, which is one component of the composition, uses the above-mentioned modified PVA as a protective colloid. It is limited to being a combination.

This is because the vinyl ester polymerization system becomes a stable aqueous dispersion with RV protective colloid, but among the vinyl ester polymerization systems, vinyl ester-ethylene copolymer is especially
It shows good properties as a mixture of materials No. 11 and is expected to be used for various purposes in the future.

The vinyl ester used in the present invention has 1 carbon number.
Examples of examples in which fatty acid vinyl esters of ~1B are used include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, 2.2.44 vinyl tetramethylvalerate, saturated branched fatty acid vinyl having an average carbon number of 10 (trade name) V
vinyl acetate, vinyl propionate, and Vaova-10, either alone or in a mixture thereof, are preferably used. Vinyl monomers capable of co-forming with vinyl esters can be co-combined. For example, ethylene, propylene, vinyl chloride,
Vinylidene chloride, divinylbenzene, acid, methyl lylate.

Ethyl acrylate, butyl acrylate, acrylic lll
Acrylic acid alkyl esters such as 122-ethylhexyl, methyl methacrylate, butyl methacrylate, methacryl@2-ethylhexyl, methacrylic acid esters such as glycidyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, acrylamide, N-methylol acrylyl t%: triallyl cyanurate, diallyl phthalate, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, zero dialkyl maleate or half ester, sodium vinyl sulfonate, sodium allyl sulfonate, etc. .

Vinyl ester-rich or co-polymerized aqueous dispersions are obtained by conventional emulsion polymerization techniques. However, co-merging with ethylene and propylene is carried out under high pressure. The polymerization catalyst is a water-soluble single catalyst or a water-soluble catalyst system used in ordinary emulsion polymerization, such as hydrogen peroxide alone or hydrogen peroxide and an oxycarboxylic acid such as tartaric acid, citric acid, or ascorbic acid.
Shu-1 sulfuric acid and its salts, combinations with oxidialdehydes, water-soluble iron salts, etc., persulfates.

Percarbonates, perborates, etc. are applicable.

The present invention is characterized by mixing a pigment with the aqueous dispersion of the vinyl ester rich agglomerate and co-aggregate obtained in this way, and the pigment used in the present invention includes generally commercially available paints, 9 paper-processed paints, It can also be applied to materials used in ink, plastics, etc. For example, inorganic pigments include those mainly composed of elemental monomers (D, Zn, Pb, etc.) such as carbon black and aluminum powder.
, ffi, 84. (3d, Fe.

M3.8b-width, M1. Ba, C3m, 8i, Co, O
oxides such as r, sulfate groups, sulfides, chromates, silicates, hydroxides.

Organic pigments include natural dye pigments, nitroso pigments, nitro pigments, azo pigments, butalocyanine pigments, and basic dye pigments.

Other ingredients include quinacridone red, quinacridone violet, perylene red, and perylene carlet. Examples include dioxazine violet and isoindolinone yellow.

The amount of these pigments to be used is 1031 k parts to song parts per 100 blood parts of the solid content of the aqueous dispersion.

If the amount is less than 10 parts, the characteristics of the aqueous dispersion will not be utilized, and there will be no discernible difference between the pigment mixture and the conventional aqueous dispersion of vinyl ester iris and copolymer using PV as a protective colloid. If the amount of pigment used is 800 parts by weight or more, the mixed liquid may thicken and be difficult to handle.

The composition obtained in this way forms a clean film with no cracks after application and dries, exhibiting strong properties, and is used in a wide range of paints such as flat paints, lysine paints, mastic paints, waterproof paints, etc. You will be able to
It has also become possible to use it as an internal additive in paper processing. In particular, in the present invention, the composition of ethylene-vinyl ester co-Makura dispersion and inorganic pigment has good film-forming properties and forms a stretchy film despite having a large pigment composition, and is suitable for industrial applications such as waterproof coatings. The utility value is high.

Next, the present invention will be described in more detail with reference to Examples. In the Examples, "parts" and "%" are based on weight unless otherwise specified.

Example 1 (1.3 mol% of Sakai Oba 10 (Shell Company trademark: branched fatty acid vinyl ester with an average carbon number of 10) as a component)
, ■) Vinyl acetate ester component (D9
7.9 mol% is genated and 4g6 at 20°C
Solid modified PV film 45 with an aqueous viscosity of 50 centipoise
part, acetic acid) 13um 0. s part 1 sodium bicarbonate 0
．． 27 parts of tartaric acid, 0.5 parts of tartaric acid, and 585 parts of water were put into a polymerization reactor and dissolved by heating.While stirring, 042 parts of vinyl acetate was put into a mononitrogen gas atmosphere, and 14 parts of hydrogen peroxide was added.
Add 8 parts of the aqueous solution to start polymerization. The aqueous hydrogen peroxide solution is then added continuously at 47 parts over 2.5 hours. Once the polymerization has started, 419 parts of vinyl acetate are continuously added over 2 hours to advance the polymerization.

During this time, the internal temperature is maintained at 70 to 75°C.

After addition of vinyl acetate, keep the internal temperature at 70-75℃ for 45 minutes.
Keep it to complete the blood match. The resulting aqueous dispersion was a clear vinegar emulsion with a solid content of 41B96 and no coarse particles. The Brookfield viscosity of the aqueous dispersion at 30° C. and 12 revolutions/minute was 22,400 centivoise.

To 100 parts of this aqueous dispersion diluted to a solid content of 30 dollars, 5M parts of dibutyl phthalate was added and mixed.
After leaving it in the sun, add calcium carbonate (Sankyo Seifun KN, ii!
,, special grade) was mixed to form a stable composition. When this film was made into a film, there were no cracks during drying, and the strength and elongation of the film was as shown in Table 1, and it was strong and had good water resistance. This was found to be significantly different from the conventional PV film shown in Comparative Example 1.

Example 2) Contains 1.0 mol% of Beoba 10 (Shell Chemical Co., product δ) as a component, (contains S, O mol% of itaconic acid as a homogeneous component, 96.0 mol% of vinyl acetate as a Q component) Then, we synthesized a modified PV film in which 96.5% of the vinyl ester component was hydrogenated.
The viscosity of the aqueous solution was 5.6 centiboise.

Next, 58 parts of the modified PV membrane and 860 parts of ion-exchanged water were placed in an autoclave equipped with an electromagnetic rotary stirrer and a temperature-controllable jacket, and the mixture was stirred and heated to dissolve. After cooling,
1,220 parts of vinyl acetate monomer was added to the system while stirring, and ethylene gas was further introduced to increase the pressure to 45 kliA at 111 steps, and the temperature inside the system was raised to 60°C. At a temperature of 60° C., an aqueous hydrogen peroxide solution and an aqueous sodium pyrosulfite solution were added and emulsified for 3 hours, and after completion of the emulsification, the pH was adjusted to 6.0 with an ammonia aqueous solution. Obtained ethylene-
The aqueous dispersion of vinyl acetate has no coagulum, has a solids concentration of 50.9%, and an ethylene content of 7.2ffi1%, 50%.
Brookfield viscosity in °C is 1 at 60 revolutions/min
75-1! It was an aqueous dispersion with good mechanical stability and storage stability. When 150 parts of calcium carbonate was mixed with 100 parts of the aqueous dispersion to obtain a solid content of 3096 by adding water to the aqueous dispersion, a stable composition was obtained. When this film was made into a film, no cracks occurred during drying, and its normal performance and water resistance and elongation were as shown in Table 1 (it was strong and had good water resistance. Conventional PV
Table 1 shows the film properties of the ethylene-vinyl acetate aqueous dispersion composition corresponding to the composition of the present invention, and it is clear that the product of the present invention exhibits excellent properties.Example 5 Example 2 Talc (crown talc) is added to 100 parts by weight of an ethylene-vinyl acetate aqueous dispersion having a solid content of 5096.
Table 1 shows the properties of the film prepared by mixing 166 parts by weight.

Example 4 10G of the aqueous ethylene-vinyl acetate dispersion in Example 2 was added with 518. ? li! The film produced by mixing was extremely strong and free of cracks. In addition,
When the aqueous dispersion of the comparative example was mixed with the same amount of titanium oxide, a film with cracks was obtained.

Example 5 Ethylene-vinyl acetate aqueous dispersion 10 in Example 2
Clay (manufactured by Miyatani Kogyo, special grade clay) 82.2
The film produced by combining the gold with gold was strong and had no cracks. In addition, when the aqueous dispersion of the comparative example was mixed with the same amount of clay, a film with cracks was obtained.

Example 6 Ethylene-vinyl acetate aqueous dispersion 10 in Example 2
The film prepared by mixing 0 parts of aluminum hydroxide with 116 parts of Alt hydroxide (Kishida Chemical Reagent) was strong and free of cracks. In addition, when the aqueous dispersion of the comparative example was mixed with the same amount of aluminum hydroxide, a film with cracks was obtained.

Example 7) 1.0 mol% of dodecyl vinyl ether as a component,
A modified PV film containing 5.0 mol % of itaconic acid as the component (B) and 96.0 mol % of vinyl acetate as the 0 component, in which 97.9 g6 of the vinyl acetate ester component was converted into a gen, was synthesized. The viscosity of the 4% aqueous solution at 20°C is 7.8
It was centiboise. An aqueous dispersion was prepared in the same manner as in Example 2. ! The resulting ethylene-vinyl acetate aqueous dispersion had a solids concentration of 48.9% and an ethylene content of 1.
Brookfield viscosity at 50° C. and 7.6% irises was 188 centipoise at 60 revolutions/min. This aqueous dispersion and calcium carbonate were mixed in the same manner as in Example 2, and the properties of the film were measured.

Comparative Example 1 In Example 1, average polymerization [17
When an aqueous dispersion was prepared using polyvinyl alcohol with 0O and a degree of genification of 88%, the solid content concentration was 44.5*,
Brookfield's viscosity at 30°C and 12 rotations is 18! ! An aqueous dispersion of one centiliter was prepared. This aqueous dispersion was mixed with dibutyl phthalate and then mixed with calcium carbonate in the same manner as in Example 1 to form a film, but it was brittle and a good film could not be obtained.

Comparative Example 2 In Example 2, an aqueous dispersion was prepared using ordinary partially hydrogenated polyvinyl alcohol (20 U, aqueous solution viscosity at 4% of 5 centipoise) instead of the modified PV film, and the solid content was 55.2% and 30%. A Brookfield viscosity of 220 centiguis at 60° C. was obtained. After adding water to the aqueous dispersion to give a solid content of 30g6, add 1 part of calcium carbonate to 100 parts of the aqueous dispersion.
A film was prepared by mixing 66 parts.

Table 1 Properties of film March 24, 1982 Haruki Shimada, Commissioner of the Patent Office 1.Display of the incident Patent application 1988-188731 , name of invention pigment composition 1621 Sakazu, Kurashiki City (10g) Rishi Co., Ltd. Representative + 4 Tsuguo Hayashi Mukuoka 4. Agent 2045-1, Aoeyama, Sakazu, Kurashiki City 6. Contents of amendment The specification section IIF% and scope of claims are corrected as follows.

“Claims (1) (A) Monomers selected from the group consisting of fatty acid vinyl esters having 6 or more carbon atoms, alkyl vinyl ethers having 6 or more carbon atoms, and α-olefins having 6 or more carbon atoms. A copolymer comprising at least one of the three essential components, (B) at least one ethylenically unsaturated carboxylic acid or its lower alkyl ester or Fi acid anhydride, and (q vinyl acetate) is saponified in an alcohol solution. An aqueous dispersion of a vinyl ester copolymer containing a polyvinyl alcohol copolymer obtained as a protective colloid.

A preparative composition containing an unsaturated carboxylic acid or its low-alkynyl alcohol copolymer as a carrier colloid.

The monoester may be a diester or an acid anhydride, a methyl ester or dimethyl maleate, or the aqueous dispersion may be vinyl acetate or vinyl acetate.

Claims (1)

[Scope of Claims] (1)) Fatty acid vinyl esters having 6 or more carbon atoms, alkyl vinyl ethers having 6 or more carbon atoms, and 6 or more carbon atoms.
At least one half-cap selected from the group consisting of the above a-olefins, and at least one ethylenically unsaturated carboxylic acid or its lower alkyl ester or acid anhydride, and 0 vinyl acetate are essential. A vinyl ester or vinyl ester copolymer aqueous dispersion containing a polyvinyl alcohol copolymer obtained by saponifying a component copolymer in an alcohol solution as a storage colloid. (2)) The component is a branched fatty acid vinyl ester in which the carboxyl group is present at the a-position relative to the 5th or 4th class carbon atom, and the 0 component is ethylenically unsaturated dicarkynoic acid or its lower alkyl Claim 2, wherein the monoester is a diester or an acid anhydride, and (3) component (B) is maleic acid, maleic acid dimethyl ester, maleic acid dimethyl ester, or maleic anhydride.
Pigment composition as described in section. (4) The pigment composition according to claim 2, wherein the component (c) is itaconic acid. (6) The pigment composition according to claim 1, wherein the vinyl ester or vinyl ester copolymer aqueous dispersion is a vinyl acetate or vinyl acetate copolymer aqueous dispersion. (6) The pigment composition according to claim 5, wherein the vinyl acetate or vinyl acetate copolymer aqueous dispersion is a vinyl acetate-ethylene copolymer aqueous dispersion. (7)) Fatty acid vinyl esters with 6 or more carbon atoms, alkyl vinyl ethers with 6 or more carbon atoms, and 6 or more carbon atoms
At least one monomer selected from the group consisting of the above a-olefins, at least one type of ethylenically unsaturated carboxylic acid or its lower alkyl ester or acid anhydride, and vinyl acetate are essential. A pigment composition prepared by mixing a polyvinyl alcohol-based copolymer obtained by acetylating a component copolymer in an alcohol solution as a protective colloid with an aqueous dispersion of vinyl ester or vinyl ester co-arrangement and a pigment. °.