JPH03221571A - Production of pigment ink - Google Patents

Abstract

PURPOSE:To obtain the subject pigment ink excellent in dispersion stability of pigment particles and free from occurrence of coating spots, etc., due to pigment spots by kneading polyvinyl butyral, a plasticizer and a pigment, dissolving the kneaded material in a solvent for polyvinyl butyral and dispersing the pigment particles. CONSTITUTION:Together with 100 pts. wt. polyvinyl butyral, preferably 20-45 pts. wt. plasticizer (e.g. dibutyl adipate) and preferably 25-60 pts. wt. pigment (preferably having <=2.3mum primary particle size) are kneaded and the resultant kneaded material is dissolved in a solvent (e.g. ethanol or methyl ethyl ketone) for polyvinyl butyral in order to disperse the pigment particles, thus obtaining the objective ink.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention relates to a method for producing a pigment ink using polyvinyl butyral as a binder. The present invention relates to a method for producing a pigment ink that does not cause coloring spots such as coating spots or printing spots due to pigment spots when coated or printed on an intermediate film, and does not impair the transparency of the intermediate film.

[Prior Art] Conventionally, so-called laminated glass, in which an interlayer film made of transparent plasticized thermoplastic resin, such as plasticized polyvinyl butyral, is laminated as an intermediate layer between two glass plates, has been used for the front of automobiles. It is widely used for glass and building window glass.

If a transparent and uniform colored band or blurred colored area is applied to part or all of the surface of the laminated glass used for such purposes, it can be used as an anti-murmur effect in automobiles or as a window for buildings. However, since it is expected that the continuous light and heat shielding effects will be improved in glass laths, various methods for producing colored laminated glass having a colored band or a four-step colored area have been studied and proposed.

There are two main methods for producing colored laminated glass: one is to laminate an uncolored open film on colored glass, and the other is to laminate a colored open film with a colored band between two sheets of untinted glass. However, the former method, in which a colored band of glass is printed and fired to vitrify it, requires special equipment such as a firing furnace, and has the drawbacks of poor quality of the colored band and poor productivity.

In the latter method, one way to obtain a thin open film with a colored band is to apply or print a coloring ink on the surface of the open open film, but the ink used in this case is dye-based. From the viewpoint of weather resistance, pigment inks that use pigments as colorants are more desirable than dye inks that use pigments as colorants.

However, since conventional pigment inks have poor dispersion stability of pigment particles, colored interlayer films using these inks inevitably cause pigment spots 7F to occur in the colored bands, thus impairing the transparency of the colored bands. There was a problem.

F Problems to be Solved by the Invention] The present invention aims to provide a method for producing pigment ink that can be suitably used for producing colored laminated glass. Excellent, when a colored band is provided by printing on a polyvinyl butyral interlayer film for laminated glass, pigment spots, coating unevenness,
To provide a method for producing pigment ink that does not cause coloring spots such as printing spots and does not impair transparency.

As a result of intensive studies to solve the above problems, the present inventors have discovered that an ink produced by kneading a pigment used as a coloring agent with Pine Goo (polyvinyl butyral) and a plasticizer, and dissolving this in a solvent. This invention was completed based on the knowledge that the ink has excellent dispersion stability and is suitable for coloring ink for polyvinyl butyral interlayer films.

1 Means to Solve the Problem 1 The gist of the present invention is to knead polyvinyl butyral (hereinafter abbreviated as rPVBJ), a plasticizer, and a pigment, and use this kneaded composition to dissolve the polyvinyl butyral. 91. A method for producing a pigment ink, which is characterized by dissolving pigment particles in a solvent capable of dispersing the pigment particles.

The present invention will be explained in detail below.

In the method for producing pigment ink according to the present invention, P to r
B. It is necessary to knead the plasticizer and pigment.

There are no particular limitations on the PVB as long as it is of the same kind as the conventionally known PVB used for manufacturing inner membranes for laminated glasses. A typical example is a degree of butyralization of 60)
Examples include those having an average polymerization degree of 800-.3000 at 775 mol%.

Similarly, as the plasticizer, conventionally known ones used in the intermediate production of PVB for laminated glass can be used, and suitable plasticizers include butyl adipate, non-n-hexyl adipate (DI-IAI dicarboxylic acid esters,
Examples include polyester ethers such as diethylene glycol dibenzoate and triethylene glycol no (2-ethyl) butyrate (3GHL tetraethylene glycol no hexa7ate).

Also, there are no pigments! pigment, with W9. Fruit pigments or mixtures of these can be used, but inorganic pigments
- It is preferable that the average particle diameter of large particles is 2.3 μm or less. Since m-based pigments can be micronized to a desired particle size by applying shearing force during kneading, commercially available pigments can be suitably used.

The mixing ratio of PVB, plasticizer, and pigment is not particularly limited, but generally, plasticizer@i to 100 parts by weight of PVB
750 parts by weight, preferably 20-745 parts by weight, and 80 parts by weight of pigment 20', preferably 25-60 parts by weight.
It is preferable to use parts by weight. The proportion of the plasticizer and the proportion of the pigment can be appropriately selected from the above ranges, taking into consideration the degree of shearing force applied during kneading, the adhesive strength with the glass surfaces to be laminated, and the like.

In the method for producing pigment ink according to the present invention, the mixture consisting of PVB, plasticizer, and pigment is kneaded at a temperature higher than the softening temperature of the mixture, so that the composition of the mixture is uniform throughout, and the volume average of pigment particles is Diameter is 2.3μ
m or less, volume 99% v71. The composition of the mixture, kneading temperature and kneading time are preferably set so that the maximum product diameter is 4.8 μm or less. - Inside the shell, the composition of the mixture is within the above range, and the kneading temperature is 80. 150℃ range,
The kneading time depends on the performance of the kneader used, but can be in the range of 10-30 minutes when using commonly used mill rolls, batch niegoos, and extrusion mills. Of course, the type of kneading machine to be used is not limited to those mentioned above, and any type of kneading machine capable of applying shearing force to the softened mixture may be used. Furthermore, before kneading the above mixture, it is preferable to dry mix the PVB, plasticizer, and pigment.

In the yi method of the pigment ink according to the present invention, the pigment ink is homogenized by a kneading operation using a kneader, and the volume average diameter is 2.
．． The desired pigment ink can be obtained by dissolving in an organic solvent a kneaded composition in which pigment particles are finely divided to about 3 μm or less and a 99% volume cumulative maximum diameter of 4.8 μm or less.

The organic solvent used at this time may be one that is soluble in PVB, and should be selected in consideration of the coating/printing characteristics and drying characteristics of the obtained ink on the surface of the open film.

Typical solvents for ink include ethanol, flobyl alcohol, methyl alcohol, cyclohexanol, methylcyclohexal, methyl ethyl ketone, cyclohexane, isopropyl ether, dithyl butyl ether, tetrahydro-7, and the like. I can do it.

When these solvents are used, the entire amount of PVB and plasticizer contained in the kneaded composition can be completely dissolved with approximately 10 times the amount of solvent on a weight basis, and the target pigment can be completely dissolved. It may be determined as appropriate depending on the concentration and the like.

[Effects of the Invention 1 The present invention has the following particularly remarkable effects, and its industrial utility value is extremely large.

(1) According to the method of the present invention, P as the ink vehicle
When the VB, plasticizer, and pigment are kneaded, the pigment is made fine, so there is no need to use a particularly fine pigment as a starting material.

(2) The method of the present invention does not involve the difficulty of dispersing secondary agglomerated pigment powder, which is encountered when using particularly fine pigments as starting materials.

(3) The pigment ink obtained by the method of the present invention has excellent dispersion stability of pigment particles, and when a colored band is provided by coating or printing on a polyvinyl butyral interlayer film for laminated glass, pigment spots and coating are applied to this colored band. An interlayer film having a colored band with excellent transparency and V without coloring spots such as spots and printing spots can be obtained.

Example 1 The present invention will be explained in more detail with reference to Examples, Comparative Examples, and Reference Examples. However, it goes without saying that the present invention is not limited to the following examples unless it exceeds the gist thereof.

In addition, in the following examples, the particle size measurement of the pigment particles (volume average diameter, 99% volume cumulative maximum diameter), inspection of the presence or absence of pigment spots, and measurement of the transparency of the colored interlayer film were carried out by the following method. .

Measurement of Particle Size of Pigment Particles 1 part by weight of the obtained pigment ink was mixed with 20 parts by weight of a plasticizer (
A sample diluted with non-n-hexyl anovate, DNA) was used as a measurement sample, and a laser light scattering particle size analyzer (L
Microtrack-3PA (manufactured by eed & Northrup) was used to measure the volume average diameter and volume of 99%.
The cumulative maximum diameter was measured.

Vertical heather! The laminated glass laminated with a colored interlayer film using the obtained pigment ink was placed on a transparent glass viewing table and illuminated with a 20W fluorescent light from below the viewing table. The presence or absence of pigment spots was observed with the naked eye.

Luxury 1 position gty > Layer weight 1 A laminated glass laminated with a colored interlayer film using the obtained pigment ink was used as a sample, and it was transferred to an automatic machine.
Tokyo Juishiki Co., Ltd. S! ! , using TC-HI[1DP),
According to JIS K7105, haze value (monovalent, %
) was measured.

Example 1 1) Pigment ink IIl! Production and Evaluation A mixed composition obtained by dry mixing 100 parts by weight of PVB, 35 parts of a plasticizer, and 50 parts of the following MI& brown pigment was mixed with a 100% The solid content of the ink was prepared by kneading for 10 minutes at ℃.

Composition of dark brown pigment> Carbon blank 1 part by weight CI P
igment Red 207 1 part by weight CI
Pient Yellow 110 1 part by weight Next, the solid content of the ink obtained by 1II9I as described above was dissolved in 10 parts by weight of methyl ethyl ketone per 1 part by weight of this solid content to obtain a brown pigment ink. Regarding this pigment ink, when the particle size of the pigment particles was measured by the Fuki force method, the volume average diameter was 1.7 μm, and the cumulative maximum diameter at 99% volume was 3.5 μm.

2) Preparation and evaluation of colored interlayer film and laminated glass Next, 5ml of brown pigment ink prepared as above
was uniformly coated on a PVB interlayer of 300 square meters and 0.76 mm thick using bar coater #3, and heated at 60°C for 1 hour.
After drying for a minute, a colored interlayer film was obtained. This colored interlayer film
A colored laminated glass was produced by laminating two glass plates with a thickness of 2.51 cm, and heating and pressing them using a flat plate press at 135° C. and 13 kg/cm 2 .

This colored laminated glass was examined for pigment spots using the method described above, but no pigment spots were observed. Further, when the transparency was measured by the above method, the haze value was 3.8%, indicating good transparency. These results are summarized in Table 1.

Comparative Example 1 In the example described in Example 1, when preparing the pigment ink,
A pigment ink was prepared in the same manner as in the same example, except that a mixture consisting of 100 parts by weight IL of PVB, 35 parts of plasticizer, and 50 parts of brown pigment was only dry mixed, and the mixed composition was not kneaded at all. 1JiI production and evaluation, and the production and evaluation of colored interlayer films and laminated glass. The results are shown in Table 1.

Example 2-・214, Reference Example 1) 73 In the example described in Example 1, the blending ratio of PVB, plasticizer, and brown pigment, the ratio of kneaded ink solid content to solvent, and kneading conditions were changed, respectively! vl! LiIgl and evaluation of pigment ink, and preparation and evaluation of colored interlayer film and laminated glass were carried out in the same manner as in the same example except for the changes shown in Table 11. The results are summarized in Table 1.

Examples 15' and 17 In the example described in Example 1, mill rolls (
Manufactured by Minamisenju Seisakusho, 601φ×460mmL, Example 15
〉, Extruder (manufactured by Toyo Seiki Co., Ltd., D20-25, Example 16), Nigu (manufactured by Irie Seisakushin Co., Ltd., PNV-5)
Preparation and evaluation of pigment ink, upper V colored interlayer film,
Created and evaluated laminated glass. The results are also shown in Table 1.

! From Table 11, the following is clear.

(1) If the kneading of the ink solids, which is essential in the method of the present invention, is omitted, the pigment ink with practical value is
! ! ! Can not.

(2) ml! by the method of the present invention! The pigment ink is
The pigment is finely divided during kneading, making it extremely suitable for producing a colored interlayer film of good quality.

(3) When using the method of the present invention, there is no need to use a particularly fine pigment as a starting material.

(・t) When using the method of the present invention, there is no need for a special kneading rock, and various commonly used kneading rocks can be used. Furthermore, since no special pigment grinding process is required, the manufacturing process is simple.

(5) In the method of the present invention, the particle size of pigment particles in the ink and the transparency of the colored interlayer film can be easily controlled by selecting and combining the proportion of the pigment in the ink solid content and the kneading conditions. .

Claims (4)

[Claims] (1) A method for producing a pigment ink, which comprises kneading polyvinyl butyral, a plasticizer, and a pigment, dissolving the kneaded composition in a solvent that can dissolve the polyvinyl butyral, and dispersing the pigment particles. (2) The method for producing a pigment ink according to claim (1), wherein polyvinyl butyral, a plasticizer, and a pigment are dry mixed in advance, and the mixture is kneaded while being maintained at a temperature selected from the range of 80 to 150°C. (3) The method for producing a pigment ink according to claim (1) or (2), wherein the proportion of the plasticizer to 100 parts by weight of polyvinyl butyral is 15 to 45 parts by weight. (4) Pigment particles in the pigment ink have a volume average diameter of 2.3μ
The method for producing a pigment ink according to claim (1), (2), or (3), wherein the pigment ink has a maximum diameter of 4.8 μm or less and a 99% volume cumulative maximum diameter of 4.8 μm or less.