JPH0238440A - Colored acrylic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in transparency, uniformity and coating characteristics by mixing a specified acrylic resin with a solvent, a colorant and a dispersant which is a derivative of an organic colorant. CONSTITUTION:1-30wt.% methacrylic acid is reacted with 10-40wt.% butyl acrylate, 30-70wt.% butyl methacrylate and 0-20wt.% other monomers to obtain an acrylic resin (A). 10-50wt.% component A is mixed with a solvent (B) (e.g., ethyl Cellosolve), 1-30wt.%, based on component A, colorant (C), desirably, a pigment (e.g., copper phthalocyanine) and 0.1-30wt.%, based on component C, dispersant (D) which is a derivative of an organic colorant (e.g., copper phthalocyanine derivative).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an acrylic resin coloring composition used as a heat-resistant ink, a heat-resistant paint, or the like.

<Purpose of the invention> Acrylic resin has excellent heat resistance and transparency, so by adding heat-resistant dyes or heat-resistant pigments and making it into ink, it can be used as a coloring composition for heat-resistant paints, single-color filters, and color separation filters. It can be used as an object.

<Prior Art> Conventionally, color separation filters and the like have been created by dissolving dyeable organic substances in water and repeating patterning, dyeing, etc. However, the organic substances used are purified natural products such as gelatin and casein, and these natural organic substances have the disadvantage of poor heat resistance. Furthermore, the dye used for coloring is also susceptible to discoloration or fading when heated. In order to improve this heat resistance, various methods of coloring with pigments have been investigated, but the dispersibility of the pigments is difficult and it is not possible to create a colored composition with good transparency and uniformity, so it is difficult to make a coloring composition that is practical. It was not possible to create a decomposition filter.

<Problems to be solved by the invention> As mentioned above, as a raw material for color separation filters, it is necessary to disperse pigments uniformly and stably in acrylic resin with good heat resistance and light resistance, and to achieve transparency and uniformity. By providing a composition with excellent properties and coating properties, the present invention provides a colored composition that can be used, for example, in color separation filters.

<Structure of the Invention> That is, the present invention comprises an acrylic resin composition whose main components are an acrylic resin, a solvent, a dye, and a dispersant that is a derivative of an organic dye.

The main component of acrylic resin is CH methacrylate.

(CHz□CH-Cool), butyl acrylate (C
Hz-CH-C4CH.

R9), methyl methacrylate (CHz=C-COO
Polymers consisting of CHs) can be mentioned. The composition ratio is 1 to 30% by weight of methacrylic acid, 10 to 40% by weight of butyl acrylate, and 30 to 30% by weight of butyl methacrylate.
It is an acrylic resin whose main component is 70% by weight.

However, the components are not limited to these, and some or all of them may be replaced with similar compounds.

Alkyl acrylates having an alkyl group having 1 to 5 carbon atoms or branched alkyl acrylates can be used instead of butyl acrylate. In addition, as a substitute for methyl methacrylate, there are alkyl methacrylates having an alkyl group having 1 to 5 carbon atoms, branched alkyl methacrylates, and the like. Also included are polymers formed by adding small amounts (0 to 20% by weight) of one or more monomers to these compositions.

These monomers that can be added in small amounts include methyl acrylate, methyl methacrylate, butyl acrylate, cyclohexyl acrylate, dimethylaminoethyl methacrylate, hensyl acrylate-1, glycidyl methacrylate, styrene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, and tetrahydrofurfuryl. Examples include methacrylate.

Examples of the solvent include methanol, ethanol, methyl cellosolve, ethyl cellosolve, etc., and mixtures of these solvents may also be used, but ethyl cellosolve is particularly preferred from the viewpoint of coating properties.

Although dyes and pigments can be used as the dyes according to the present invention, pigments are preferable from the viewpoint of heat resistance.

Heat-resistant pigments include barium sulfate, zinc white, lead sulfate, titanium oxide, yellow lead, red iron oxide, ultramarine blue, &tt
No additives such as blue, chromium oxide, carbon black, Benzidine Yellow 01 Benzidine Yellow GR, Resolforst Orange 3GL.

Palkan Fast Orange GG, Pigmenless Scarlet 3B, Thioindigo Maroon, Phthalocyanine Blue Phthalocyanine Green, Indan Stremburu,
These include green gold and macarite green lake.

The dispersant according to the present invention is a derivative of an organic dye, and the base organic dyes include azo, phthalocyanine, quinacridone, anthraquinone, perylene, perinone, thioindigo, dioxazine, isoindolinone, These include quinophthalone, triphenylmethane, and metal complex salts. Substituents for these organic dyes include a hydroxyl group, a carboxyl group, a sulfonic acid group, a carbonamide group, a sulfonamide group, or any substituent represented by the following formula. A derivative having at least one substituent selected from these substituents is used.

General formula CHI --X-A (X: oxygen or sulfur atom, A-niaryl group) (x: alkylene group, R3, Rz: hydrogen atom or alkyl group, or R6 and R2 together are a heterocycle containing at least a nitrogen atom) (R,: hydrogen atom, alkyl group or allyl group, R2:
(R1: hydrogen atom or alkyl group A: alkylene group, R2: alkyl group, alkoxyalkyl group or cycloalkyl group, R1: hydrogen atom) .

(a cycloalkyl group, or a heterocycle containing at least a nitrogen atom between R2 and R3) Note that the dye and the parent organic dye of the dispersant are usually the same in combination due to the relationship of hue, but they are not necessarily the same. There's no need.

In the composition of the present invention, the composition ratio is not particularly limited, but usually the acrylic resin is about 10 to 50% by weight based on the composition, and the ratio of the pigment varies depending on the type of acrylic resin and the type of pigment. , 1 to 3 for acrylic resin
The content of the dispersant is approximately 0.1 to 30% by weight based on the pigment, although it varies depending on the type of pigment. Furthermore, the colored composition of the present invention can also be used as a color concentrate with a high pigment content. Incidentally, additives may be added if necessary.

To make paints, inks, etc. based on the present invention, acrylic resin, solvent, pigment, and dispersant are processed by roll mill, ball mill, etc.
Disperse and mix using sand mills, attritors, and other dispersing and mixing equipment. Alternatively, it can also be made by dispersing the acrylic resin, pigment, and dispersant in advance using a roll mill or the like, and then diluting it with a solvent or a varnish made of the acrylic resin and the solvent. Also, by mixing pigments and dispersants,
Next, it can also be mixed and dispersed with varnish or the like. In addition,
The order of mixing and dispersion is not limited to this, but can be performed as appropriate.

A colored film of any thickness can be obtained by applying the dye, ink, etc. obtained as described above onto the object using a roll coater, spin coater, or the like.

Since the present invention uses an organic dye derivative as a dispersant, it has excellent dye dispersion and dispersion stability over time.
Since a well-colored product can be obtained, it is suitable for producing color separation filters, and can also be used for electronic parts such as color copies.

Next, the present invention will be explained in more detail with reference to Examples. "Part" indicates part by weight.

<Example 1> After completely dissolving 10 parts of copper phthalocyanine in 100 parts of chlorosulfonic acid in a four-eye flask equipped with a stirrer, a reflux condenser, and a thermometer, 21 parts of thionyl chloride was added, and the temperature was gradually increased. Warm and keep at 112-113°C for 4 hours. After cooling, pour into ice and rinse with ice water. Transfer this paste to a four-eye flask equipped with a reflux condenser, and add 10 ml of water.
Add 0 parts, 21 parts of N,N-diethylaminoethylamine, stir at room temperature for 12 hours, and then heat at 60"C for 1 hour. After the reaction is complete, filter, wash with water, and dry to obtain a blue powder of copper phthaloniacin derivative. As a result of elemental analysis of this blue powder, the analysis values returned to those of a derivative into which about three substituents C, I+ 5 C, and Hs were introduced.

The above mixture of 0.1 part of copper phthalocyanine derivative and α-type copper phthalocyanine pigment and 16.5 parts of acrylic resin (20 parts of methacrylic acid, 30 parts of butyl acrylate, and 50 parts of methyl methacrylate were dissolved in 300 parts of methyl cellosolve, and under nitrogen atmosphere azobisisobutyronitrile 0.75
50 parts of acrylic resin and 150 parts of methyl cellosolve obtained by reaction at 70"C for 5 hours were kneaded using a three-roll roll. The viscosity at 25°C during kneading was measured using a BM type viscosity needle. 6, the viscosity was 586 cps.Also, this product was left standing at room temperature for one week, but the viscosity was 586 cps.
1 cps, and no color separation or sedimentation was observed.

<Example 2> In a container equipped with a stirrer, 100 parts (dry weight) of a press cake of unsubstituted α-quinacridone and an average of two N-(2-carboxy-5-nitrobenzoyl)amino acids having the following structure (a) were added. Add 15 parts (dry weight) of quinacridone press cake substituted with methyl groups, add water to make a slurry of about 4000 parts, add an aqueous sodium hydroxide solution to adjust the pH to 9.5, and raise the temperature to 50°C. Stir for 1 hour. After adding 10.1 parts of hydrated aluminum sulfate (8% by weight as AIJ*min), the pH was adjusted to 6, filtered, washed with water, and dried at 100°C to form a powder.

The viscosity of a paint prepared by dispersing 5 parts of this pigment composition and 50 parts of acrylic resin (same acrylic resin as in Example 1) using a three-roll roll and at 25°C after being left for one month was measured using a BM type viscometer. As a result, it showed no structural viscosity. Furthermore, the paint thus obtained provided a coating film with extremely excellent surface gloss.

<Effects of the Invention> Conventionally, it has not been possible to obtain a composition with good uniformity using an acrylic resin and a pigment, but by using a pigment derivative as a dispersion side, a stable composition with high transparency and excellent heat resistance can be obtained. I was able to get it.

The coloring composition of the present invention has excellent color separation characteristics and transparency, and is also heat resistant, so if used in a color filter for color display of a liquid crystal display device, it will exhibit excellent color characteristics and The present invention is extremely superior in practical terms, as it can withstand heat treatment that is common during the manufacturing process.

Claims (2)

[Claims] (1) An acrylic resin coloring composition containing as main components an acrylic resin, a solvent, a pigment, and a dispersant that is a derivative of an organic pigment, wherein the main component of the acrylic resin is methacrylic acid,
A coloring composition comprising butyl acrylate and methyl methacrylate. (2) The acrylic resin coloring composition according to claim (1), wherein the dye is a pigment.