JPH02245049A - Moldable acrylonitrile polymer mixture - Google Patents

Abstract

PURPOSE:To produce a moldable acrylonitrile polymer mixture which can develop a color tone of an excellent decorative effect, such as pitch-darkness or melange by mixing colored polymer beads comprising an acrylonitrile polymer with a colored acrylic fiber. CONSTITUTION:A mixed dispersion comprising an aqueous dispersion (a) of an acrylonitrile polymer comprising at least 40wt.% acrylonitrile and optionally other vinyl monomers with a pigment (b) of a particle diameter <=0.3mum is spray-dried to obtain a colored polymer beads (A) of a particle diameter of 1-100mum. Component A is mixed with a colored acrylic fiber (B) having a fiber diameter <=100mum, desirably <=40mum and a fiber length <=3mm, desirably >=1mm and desirably having a functional active hydrogen atom group in a mixing ratio A/B of (1-99%)/(99-1%) to obtain the title mixture. A coating material is mixed with 10-100 pts.wt., per 100 pts.wt. net of the coating material, above mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to molded acrylonitrile (hereinafter referred to as AN]-based polymer mixture.

(Prior Art and Problems) Conventionally, inorganic colored powders or organic polymer colored powders have been used as a method for producing color tones such as leather-like or velvety-like in paint films.

However, when the particle size of the inorganic colored powder becomes larger than about 10μ, r# abrasion resistance and severe scratch resistance tend to decrease due to the brittleness that is a characteristic of the inorganic substance itself.
Moreover, inorganic materials have various drawbacks, such as poor adhesion to organic resins that serve as a matrix, and furthermore, the inorganic materials themselves do not have ductility, resulting in reduced processability of the coating film.

As a method to eliminate such drawbacks of inorganic materials, a method using colored thermoplastic organic polymer powders such as polyethylene, polypropylene, polyester, etc. has been proposed, but such powders have poor solvent resistance, Furthermore, coating films using the powder have drawbacks such as poor weather resistance.

Furthermore, even if the above-mentioned colored powders were used, it was difficult to produce deep color tones such as jet black tone and melange tone, or to produce various color tones.

(1@Problem to be Solved by the Invention) The object of the present invention is to be able to express color tones with excellent design properties such as jet black tone and melange tone, which were difficult to express with conventional colored powders, and Solvent resistance, weather resistance, adhesion,
The object of the present invention is to provide an industrially advantageous molded AN-based polymer mixture that has no practical problems such as processability.

(Means for Solving the Problems) The above-mentioned object of the present invention is to combine colored polymer beads made of an AN-based polymer with a particle diameter of 1-100 u, and colored acrylic beads with a fiber diameter of 100μ or less and a fiber length of 3n or less. This is achieved by a shaped AN-based polymer mixture consisting of fibers.

The present invention will be explained in detail below.

The particle size of the colored polymer beads used in the present invention is t-
If the particle size is outside the above range, the coating film may not be uniform during application, or it may cause streaks on the coating film, resulting in poor processability, which may result in a failure to achieve the intended purpose. cannot be achieved.

The method for producing colored polymer beads is not limited in any way as long as the above-mentioned requirements are met, but as an industrially advantageous method for producing colored polymer beads with a predetermined particle size, for example, the following method is suitable. can be adopted.

A mixed dispersion of the AN polymer emulsion and the pigment is spray-dried.

Here, the AN-based polymer aqueous emulsion is an AN-based polymer consisting of AN alone or 40% by weight or more, preferably 60% or more, more preferably 70% or more of AN, and the balance is at least one other vinyl monomer. A polymer is dispersed in an aqueous medium. If the AN content is less than the above lower limit, the weatherability and solvent resistance will be insufficient.

Other vinyl monomers include, for example, vinyl halides and vinylidene halides; unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, and itaconic acid, and salts thereof; Vinyl esters such as vinyl acetate; vinyl sulfonic acid, p-
Unsaturated sulfonic acids such as styrene sulfonic acid, (methaneacrylic acid sulfoalkyl ester, 2-acrylamido-2-methylpropanesulfonic acid, etc.) and salts thereof; unsaturated compounds that can be copolymerized with AN, such as acrylamide and styrene.

In addition, the particle size of the AN-based polymer is determined to be 1μ or less, preferably 0.5 μm or less, considering the miscibility with the pigment, the operability of spray drying, the color tone of the finally obtained colored polymer beads, etc.
! 7 or less is desirable.

As the aqueous medium, water is usually used, but an aqueous mixed solvent containing a water-miscible organic solvent such as methanol, ethanol, acetone, etc. may also be used.

A suitable method for producing such an aqueous ANN polymer emulginone is the method described in, for example, Japanese Patent Publication No. 55-2207.

Next, the pigment has a particle diameter of J, u or less, preferably 0.5, /j or less, more preferably o, s,
tt or less, and if the upper limit of the particle size is exceeded, it will be difficult to mix and disperse the ANN-based polymer aqueous emafugidine, and only a light-colored powder will be obtained, resulting in a clear and velvety color tone. It is not possible to provide colored polymer beads that express

There are no limitations on such pigments as long as they meet the above particle size range, but in particular pigments with particle sizes of 0.8, I
! Fuji SP Yellow 4060 manufactured by Fuji Shiki ■, in which the following pigments are stably dispersed in an ethylene glycol-aqueous dispersion medium,
Suitable pigments include Fuji SP Red 5209, Fuji SP Blue 6081, and Fuji SP Black 8229.

The mixing ratio of the AN polymer aqueous emulsion and the pigment is preferably 1 to 80% by weight, preferably 5 to 40% by weight, based on the AN polymer. In this case, the object of the present invention cannot be achieved.

There are no particular limitations on the spray drying, and either a 1-pressure nozzle or a 2-fluid nozzle can be used in the dust atomizer.

The spray drying conditions when using a two-fluid nozzle include mixing a mixed dispersion with a solid content concentration of approximately 1 to 50% by weight with compressed air, atomizing it, and drying at a temperature of 50 to 220°C. is desirable.

Further, the fiber diameter of the colored acrylic fiber used in the present invention is determined depending on the thickness of the coating film, but is 100 p or less, preferably 40 p.m. a or less, and the fiber length is 8 or less,
Preferably, it is necessary that the amount is less than 1, and if the upper limit is exceeded, the intended purpose of making the coating film uniform during dispersion and application into a paint cannot be achieved.

Further, the fibers can be colored by conventional means using the pigments or any dyes mentioned above on the acrylic fibers.

and! The acrylic fiber preferably contains at least one type of functional group having active hydrogen, such as a hydroxyl group, a carboxyl group, an amide group, an amino group, a sulfonic acid group, and a sulfuric acid group. The adhesion with the paint matrix resin is improved. The content of such functional groups is desirably within the range of 0.2 to 10%, preferably 0.5 to 5%, based on the weight of the acrylic fiber, and if it is outside this lower limit, the adhesion improvement effect may be reduced. If it is small and exceeds the upper limit, the water resistance of the coating film will decrease.

The method of introducing such a functional group is not limited, and there are known methods such as copolymerizing a monomer containing a desired functional group, introducing it as a catalyst terminal, and modifying acrylic fiber (hydrolysis, reduction, etc.). may be adopted as appropriate, and some of these means may be combined.

In addition, the cross-sectional shape of the acrylic fiber can be arbitrarily adopted such as round, irregular shape, etc., but flat, eyebrow-shaped, triangular, square, Y-shaped, etc.
Irregular cross-sectional shapes such as a cross and a U-shape, particularly flat, eyebrow-shaped, and triangular shapes, are preferable from the viewpoint of the design of the coating film (sparkling feeling), etc.

As described above, the method for producing such colored acrylic fibers includes obtaining the desired AN content, functional group content, fiber diameter,
There are no limitations as long as fibers that satisfy the fiber length can be obtained, but by cutting short fibers or long fiber-like acrylic fibers with AN content and fiber diameter within the desired range to the desired fiber length. can get. Note that the coloring of acrylic fibers may be done before or after cutting, and when functional groups are introduced by modifying acrylic fibers, it does not matter whether it is colored before or after cutting. . Here, fibers are fused together during cutting (multiple fibers are cut together due to the pressure during cutting)
It is important not to cause crimping on the Jf surface, and if there is fusion, the fluidity of the paint will deteriorate, resulting in uniform coating @ft.
can't get it.

In addition, from the viewpoint of applicability (dispersibility in paint), it is desirable to attach an oil to the surface of llka.

The type of oil agent cannot be determined unambiguously because it needs to be changed depending on the type of matrix resin, dispersion medium, or solvent in the paint, but for water-based paints, for example, nonionic, anionic, and cationic oils are used. For drainage paints, hydrophobic oils such as fluorine-based and silicone-based oils are desirable. The amount of oil applied is generally within the range of 0.11 to 8% based on the fiber weight.

Note that the oiling step may be performed either before or after cutting the ultra-short fiber length, but it is preferable to apply the oil before cutting in terms of operability and avoidance of inter-fiber fusion during cutting.

In particular, in order to further improve adhesion, coatability, etc., the fiber length is Q, 5 ytttt or less, preferably Q, 8
Nil or less is desirable, and such fibers can be obtained, for example, by cutting stretched acrylic fibers and then shrinking them.

Furthermore, depending on the final use of the paint, the coating film may be required to have four functions such as flame retardancy or noncombustibility, antistatic or conductive properties, and moisture and water absorption properties. Colored acrylic fiber with the functions of
It can be used appropriately as SS.

The molded AN-based polymer mixture of the present invention can be obtained by arbitrarily mixing the above-mentioned colored polymer beads and colored acrylic fibers, and the mixing ratio of colored polymer beads/colored acrylic fibers is determined depending on the desired design, color tone, etc. 1-9
It is appropriately selected from 9%/99 to 1%, and several types of colored polymer beads and several types of colored fibers may be used in combination.

The mixture can be added to the paint by any of the commonly used methods, such as adding it during paint production and kneading it, or dispersing it in a paint diluent in advance and then adding the paint diluent to the paint. The method of Dans is adopted.

At this time, the blending ratio of the mixture to the paint is 10 to 100 parts, preferably 20 to 6 parts, per 100 parts of the pure paint.
It is desirable that the amount be within the range of 0 parts. If the lower limit of this range is applied to an external force, sufficient design effect cannot be achieved.
Moreover, if the upper limit is exceeded, the desired objective of uniformly dispersing the mixture in the paint cannot be achieved.

There are no limitations to the paint that uses this mixture, such as acrylic, melamine alkyd, epoxy thread, phenolic,
Non-aqueous paints such as polyester-based, silicon acrylic-based, vinyl-based paints, or water-based paints are used.

(Effects of the Invention) The molded AN-based polymer mixture of the present invention has excellent properties such as solvent resistance, 1 liter strength, adhesion, and processability by mixing colored polymer beads and colored acrylic fibers. The present invention provides a pigment that can express a color tone with excellent design properties such as jet black tone or melange tone, and can also provide a coating film with excellent appearance such as gloss and clarity. This is a noteworthy effect.

The molded AN-based polymer mixture thus obtained is widely used in fields such as paints as a pigment capable of expressing novel design properties.

(Implementation (j'lJ) The present invention will be explained in more detail by showing examples below.
The scope of the present invention is not limited by the description of these Examples. Parts and percentages given in the examples are by weight unless otherwise specified.

Incidentally, the adhesion A note, gloss, 1IiI'1 appearance, adhesion, sharpness and design were measured as follows.

+l+ 1liIt After drying the solvent-based colored polymer beads or colored fibers, immerse them in a mixed solvent of Kijirol/Getanol/Cyclobexane/Butylcarpitol = 40/15/15/80, and
After storage for 0°cxaoo time, the weight loss rate was measured.

(2) Heating residue 5 whose main component is a glossy acrylic ester polymer
A test paint was prepared by uniformly dispersing a predetermined amount of the molded AN polymer mixture in a 0% water-based emulsion paint. The paint was roll coated with epoxy paint as a brimer to a thickness of about 5p on a 0.85mt thick galvanized iron plate which had been subjected to normal phosphate treatment, and after baking was treated,
A coated copper plate was prepared by roll coating to a thickness of .

The gloss of this steel plate was measured using a 60 degree specular reflectance (sample).

(8) A coated steel plate was prepared in the same manner as above except that a polyester solvent paint was used instead of the water-based emulsion paint of a water-based acrylic acid ester polymer, and after 1000 hours of sunshine weather meter testing, it was tested. Using the previous steel plate as a standard plate, the color difference is △ using Hitachi's new Color Analyzer Model 307.
E was measured.

(4) Visibility and design The appearance of painted steel sheets prepared in the same manner as the above weather resistance measurement was evaluated by five experts for the clarity and design of the colors (melange, velvet, and jet black tones). A 5-level evaluation was conducted for each judge, and each judge's total score (out of 25 points) was given.

(5) Adhesion A coated steel plate prepared in the same manner as in the above weather resistance measurement was coated with a radius of 6
It was wrapped around a round rod and the state of peeling of the film was observed using a 10x magnifying glass.

○: No peeling of the film △: Some f#JN is observed ×: Severe peeling Examples 1 to 4, Comparative Examples 1 to 6 Monomers etc. of the following composition were placed in an autoclave, sealed, and stirred. After polymerization at 150°C for 20 minutes under continuous stirring, it was cooled to about 90°C, taken out from the autoclave, and emulsion (average particle size 0.0?, I
! Z) was produced.

AN 291 parts p-styrene sulfonic acid salt (SPSS) 9Gte
rt, -Butyl peroxide 1.5 Ion exchange water 700 After mixing the obtained emulsion and the pigment shown in Table 1 below so that the ratio of pigment to the polymer in the emulsion was 20%, Spray drying (using a two-fluid nozzle manufactured by Spraying System Japan Co., Ltd.) under the following conditions to obtain an average particle size of 15.
colored polymer beads (with a solvent resistance of 0.1
%) Four types were produced.

Spray transition line conditions Solid content concentration Spray drying temperature Compressed air supply rate Supply rate 80% 180°C O, 5N, rl/min 1, O1/li table Using acid, acrylamide, or methyl acrylate, eight types of AN-based polymers were prepared by varying the type and copolymerization amount of the monomers, and the polymers were spun according to a conventional method to obtain round-section acrylic. Make fiber # (fiber diameter 14, 11) and then use a Matsushita Seiki cutter! Five types of colored fibers shown in Table 2 below (solvent resistance of all 0.8%) were produced by cutting the fibers into fins with a fiber length of 0.4 and 0.1.

Table 2 The obtained colored polymer beads and colored fibers were mixed in the compositions shown in Table 8 below to produce test paints for Examples 1 to 4 and Comparative Examples 1 to 6.

Table 4 shows the evaluation results for gloss, sharpness, laziness, and adhesion.

As is clear from Table 4, the products of the present invention (Examples 1 to 4) using colored polymer beads and colored uk#lI that satisfy the predetermined conditions have good brightness, gloss, clarity, and design. Excellent in and #7 notes. .

However, Comparative Examples 118.5 and 6 using Yoryo have gloss,
It is inferior in sharpness and design, and furthermore, in No. 5, which uses colored fibers and pigments that do not have functional groups, the layer density is particularly poor. Moreover, Comparative Examples 2 and 4 using only colored polymer beads are inferior in clarity and design, and furthermore, Comparative Examples 4 using a pigment with a large particle size has poor adhesion.

From the above, by using the molded AN-based polymer mixture of the present invention, it is possible to obtain coatings that are excellent in bath resistance, T15 resistance, and excellent gloss, sharpness, and design. It is understood that a membrane appearance is obtained.

Claims (1)

[Claims] Made of acrylonitrile polymer and has a particle size of 1 to 10
A molded acrylonitrile polymer mixture comprising colored polymer beads of 0μ and colored acrylic fibers with a fiber diameter of 100μ or less and a fiber length of 3mm or less.