JPH02265728A - Preparation of colored interlayer for laminated safety glass - Google Patents

Abstract

PURPOSE:To make it possible to decrease remarkably the amt. of generation of an unnecessarily colored resin and to shorten remarkably a switching time accompanied with color change by feeding a pigment ink compsn. into a molten thermoplastic resin in a metering part of an extruder. CONSTITUTION:A raw material compsn. is transferred in a metering part A through a feeding part and a compression part of a cylinder. On the other hand, a pigment ink compsn. reaches a quantitatively pressing pump 9 from an ink tank 8 through a pigment ink filtering unit 10 and is fed into a molten thermoplastic resin in the metering part A. The pigment ink filtering apparatus 10 with a structure installed with a stirring unit and an ultrasonic vibration element as a means for preventing the pigment from sedimentation is used. The pigment ink compsn. consists of a pigment particle and a plasticizer which can be compounded with the thermoplastic resin. It is pref. that the mean particle diameter of the pigment particle is 2.5mum or smaller; the 99wt.% cumulative max. particle diameter is 5.0mum or smaller; the apparent pH of the pigment ink compsn. in the range of 4-10.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a colored interlayer film for laminated glass.

[Conventional technology]

BACKGROUND ART Laminated glass using a colored resin interlayer film is often used to suppress increases in indoor temperature due to incident light inside buildings, cars, etc., and to improve aesthetic appearance. In that case, usually
2 to ensure internal illuminance and internal transparency.
A colored interlayer film having a light transmittance of 0% or more is used.

This colored interlayer film is composed of a thermoplastic resin, a plasticizer, and a colorant, and as the colorant, it is preferable to use a pigment that has better light resistance than a dye.

Conventionally, when using pigments, powder resin, plasticizer, and pigment ink are powder-mixed to form a uniform mixture, which is then fed to the hopper of an extruder, melted and kneaded within the extruder body, and then passed through a T-die. A method of forming a film by extrusion molding is generally employed.

[Problem to be solved by the invention]

However, in the conventional method of manufacturing a colored interlayer film for laminated glass, when changing the colored interlayer film to one having a different hue, that is, when changing the color of the interlayer film, there are Since it is necessary to replace the resin in the production system, a large amount of unnecessary colored resin is generated and the yield decreases, and it also takes a long time to replace the colored resin in the extruder with another colored resin. This method has the drawback that it is difficult to efficiently produce a colored interlayer film.

The present invention has been made in view of the above-mentioned problems in the conventional technology.

Therefore, an object of the present invention is to provide a method for manufacturing a colored interlayer film for laminated glass, which allows for efficient color change of the colored interlayer film and, therefore, enables efficient production of the colored interlayer film.

[Means to solve the problem]

As a result of intensive studies, the present inventors have found that the above-mentioned conventional solution can be achieved by injecting the pigment ink composition for coloring into the molten resin flowing into the metering section of the extruder. find out that the problem can be overcome,
The present invention has now been completed. That is, the present invention provides a colored interlayer film for laminated glass by adding a pigment ink composition consisting of a pigment and a plasticizer to a plasticized thermoplastic resin and extruding it into a sheet form from a T-die of an extruder. The manufacturing method is characterized in that the pigment ink composition is injected into a molten thermoplastic resin in a metering section of an extruder.

In the present invention, the pigment ink composition used is as follows:
It consists of a plasticizer that can be blended with pigment particles and a thermoplastic resin, and the average particle size of the pigment particles is 2.5- or less, and 99-99
It is preferable that the weight percent cumulative maximum particle size is 5.0 μs or less and the apparent pH of the pigment ink composition is within the range of 4 to IO.

Further, in the manufacturing method of the present invention, when injecting the pigment ink composition into the molten thermoplastic resin in the metering section of the extruder, the pigment ink composition is filtered through a pigment ink filter device equipped with means for preventing pigment sedimentation. It is preferable to inject the pigment ink composition using a metering pump, thereby preventing unstable injection of the pigment ink composition due to the metering pump.

The present invention will be explained in detail below.

The plasticized thermoplastic resin used in the present invention is not particularly limited as long as it is a material used as an interlayer film for laminated glass, but examples include polyvinyl alcohol derivatives such as polyvinyl butyral, and ethylene-vinyl alcohol derivatives. A thermoplastic resin such as vinyl acetate copolymer mixed with a conventionally known plasticizer is used. Among these, plasticized polyvinyl butyral is most preferably used in terms of adhesive strength and impact resistance.

Examples of plasticized polyvinyl butyral include:
Butyralization degree BO ~ 75 mol% and average polymerization degree 800 ~
10 (polyvinyl butyral 100 Tin part of 10 and plasticizers such as phthalic acid esters such as dioctyl phthalate and dibenzyl phthalate, adipate esters such as di-n-hexis adipate and di(butylcarpitol) adipate, triethylene glycol)・J (2)
-Ethyl) butyrate, polyether esters such as tetraethylene glycol hexanoate, or mixtures thereof, in an amount of 20 to 50 parts by weight, can be suitably used.

On the other hand, a pigment ink composition added to a plasticized thermoplastic resin consists of a pigment and a plasticizer.

Any known pigment can be used, but it is desirable that the average particle size is 2.5a or less and the 99% cumulative maximum particle size is 5.011a or less.

When the average particle size becomes larger than 2.5 m or when the 99% cumulative maximum particle size becomes larger than 5.0 m, pigment spots tend to appear in the colored interlayer film formed.

Further, as the plasticizer, any known plasticizer can be used, but it is preferable to use the same plasticizer as that used in the plasticized thermoplastic resin. Typical examples of plasticizers when polyvinyl butyral is used include dicarboxylic acid esters such as dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, Dibutyl sebacate, di-2-ethylhexyl sebacate, di(butylcarpitol) adipate, di(hexylcarpitol) adipate, di(butylcarpitol)
Examples of polyether esters include diethylene glycol dibenzoate, triethylene glycol di(2-ethyl) butyrate, tetraethylene glycol dihexanoate, and triethylene glycol dihexanoate. Examples include butanoate, tetraethylene glycol dihebutanoate, pentaethylene glycol dihebutanoate, and the like. These plasticizers may be used alone or in combination of two or more.

In the present invention, the colored ink composition has an apparent pH of 4.
It is preferably in the range of ~IO. The apparent pH here means "measured by a pH meter using a glass electrode as a measuring electrode and an agaric electrode or a silver-silver chloride electrode as a comparison electrode". When measuring, the pH value after the pH reading has become sufficiently stable is calculated based on the apparent pH value of the composition.
Let it be H.

Note that it usually takes about 1 hour before the pH reading becomes sufficiently stable.
It takes 5 to 20 minutes.

If the apparent pH deviates from the above range, pigment spots will appear in the colored interlayer film that is formed, which is not preferable.

In the present invention, the colored ink composition may contain a pigment stabilizer.

Next, a method for producing a colored interlayer film for laminated glass according to the present invention will be described with reference to the drawings.

FIG. 1 is an explanatory diagram showing the general configuration of an extruder for carrying out the present invention.

The extruder includes a cylinder 1 having a hopper 2, a screw 3 rotated by a drive motor 4, a T-die 5 attached to the tip, and a powder mixer for supplying the raw material composition. 6. It consists of a cooling roll 7 for cooling the extruded molten film, and an ink tank 8 and a metering pressure injection pump 9 as a device for injecting the pigment ink composition into the introduction site of the metering section A. and an ink tank 8 and a metering pressure pump 9.
A pigment ink filter device 1O is provided in the flow path ti between.

When producing a colored interlayer film using this extruder,
The raw material composition mixed in the powder mixer 6 is supplied to the hopper 2. The raw material composition is passed through the screw 3.
It is transferred to the metering section A via the feed section and compression section of the cylinder.

On the other hand, the pigment ink composition reaches the metering injection pump 9 from the ink tank 8 via the pigment ink filter device IO, and is injected into the molten thermoplastic resin in the metering section A. In the metering section, the pigment ink composition and the thermoplastic resin are uniformly mixed, and the colored molten mixture is extruded into a film from a T-die 5 attached to the tip of the cylinder I, and cooled on a cooling roll 7. , rolled up in wine goo.

In the present invention, it is not necessary to provide a pigment ink filter device between the ink tank 8 and the metering pump 9, but it is preferable to use a pigment ink filter device.

As the pigment ink filter device, it is preferable to use one having a structure equipped with a stirring device and an ultrasonic vibrator as means for preventing pigment sedimentation. This prevents the pigment particles from settling within the pigment ink filter device and prevents the pigment particles from sticking to the filter surface.

FIG. 2 is a longitudinal sectional view of an example of a pigment ink filter device that can be preferably used in the present invention.
FIG. 3 is a cross-sectional view taken along line A--A in FIG. 2. In the figure, 21
is a cylindrical casing, which is fixed liquid-tightly to the substrate 22 to form a cylindrical main body.

The cylindrical body is installed on top of the electromagnetic stirring drive device 31. The upper end of the casing is an open end, where
A cap 23 having an ink introduction port 24 is screwed together, and 0
- Liquid-tightly fixed via ring 25. A filter support member 26 communicating with the ink discharge port 27 is provided inside the filter, and a filter element is removably mounted on the filter support member. The filter element includes a filter 28 made of metal mesh and a holder 29 for fixing the filter, and has a cylindrical shape with the upper end sealed by the holder. A spring 30 is attached between the holder 29 and the cap 23, and when the cap is fixed to the casing, the filter element is pressed onto the filter support base to ensure that it is supported. An electromagnetic stirrer 3 is placed on the substrate at the bottom of the casing.
2 is placed, and an ultrasonic generator 33 is placed on the side of the casing.

In the above filter device, the pigment ink composition from the ink tank is introduced from the ink inlet 24, flows as shown by the arrow, passes through the filter 28, and reaches the inside of the filter element. The pigment ink composition then descends inside the filter element, is discharged from the ink outlet 27, and is introduced into the metering pump. In the above case,
An electromagnetic stirrer 32 placed on the substrate at the bottom of the casing
is rotated by driving the electromagnetic stirring drive device 31, and the ultrasonic generator 33 provided on the side is activated, so that the pigment particles of the pigment ink composition do not settle downward and the filter It also no longer sticks to the surface of 28.

〔Example〕

The present invention will be explained below with reference to Examples and Comparative Examples.

Preparation of colored interlayer film 35 parts by weight of di-n-hexyl adipate (DIIA) was added to 100 parts by weight of polyvinyl butyral (PVB), and a Henschel mixer (Mitsui Miike Kakoki, F
Nlo-L) to prepare a raw resin composition.

Meanwhile, a pigment ink composition was prepared. That is, carbon black is used as a black pigment, and C,1,PIg is used as a red pigment.
ment blue 15:l, C8 as blue].

Pigment Red 207, and C as yellow
，! , Pfgment Yellow 110 were mixed in equal amounts to obtain a dark reddish brown mixed pigment. 5 parts by weight of this mixed pigment and 95 parts by weight of DIl^ were processed by a dispersion/pulverizer (Mitsui Miike Kakoki, Attritor HA-ID), and the pigment particles had an average particle size of 2.3 and a 99% cumulative maximum particle size. A pigment ink composition with an apparent pH of 4 was obtained with 3.3 scraps. Note that the apparent pH of the pigment ink composition is acidic,
This was carried out by appropriately selecting and mixing three types of carbon black, neutral and alkaline.

The particle diameter of the pigment particles was measured as follows. That is, the pigment ink composition was diluted with a plasticizer to form a 5% solution, and a laser scattering granulometer (Leed & Northrup
The =l'4'=I particle size and the 99% cumulative maximum particle size of the pigment particles were determined using Microtrac SPA (manufactured by Microtrac SPA).

Further, the apparent pH of the pigment ink composition was measured as follows. That is, a pH meter (manufactured by Kyoto Electronics Industry Co., Ltd., A
The electrodes (standard electrode and measuring electrode) of T-117) were placed in the pigment ink composition being stirred and left for 30 minutes to adjust the apparent pH to the value indicated by the pH meter.

These raw materials were melt-extruded using an extruder having a structure as shown in FIG. 1 to produce a colored interlayer film. That is, the above plasticized polyvinyl butyral raw material composition,
65+*mφ extruder (5HTB5-82D manufactured by Hitachi Zosen ■)
NV single screw extruder; L/D-32) (7) Supplied to hopper. On the other hand, the pigment ink composition was injected into the molten resin at the starting point of the metering section of the extruder using a metering injection pump (diaphragm type metering pump LEVA EKM-1). The injection amount of the pigment ink composition is such that when the film to be formed has a thickness of 1, the translucency is 20±.
Adjusted to show 1%.

The pigment concentration in the film at this time was 0.5% by weight. In addition, a filter device shown in FIG. 2 was installed in front of the metering pump. The molten resin extruded from the extruder is
It was formed into a film with a thickness of 1 inch using a T-die, cooled with a cooling roll, and then wound into a roll.

After confirming that the light transmittance of the colored interlayer film obtained has reached 20%, the injection of ink from the metering pump is stopped, and after the ink injection is stopped, no coloring is observed in the formed interlayer film. The time (flashout time) was measured. The results are shown in Table 1 below.

(b) For comparison, the same polyvinyl butyral (PVB), plasticizer (DNA), and pigment ink composition as in Example 1 were charged into a Henschel mixer and mixed, and the mixture was transferred to the hopper of an extruder. Then, a colored interlayer film was created. After confirming that the light transmittance of the obtained colored interlayer film with a thickness of 11111 was 20%, just before the inside of the hopper was empty, the colored ink composition was omitted and polyvinyl butyral and plasticizer (DNA) were added. The colorless mixture was poured into a hopper. The time from the start of charging until no coloring was observed in the molded interlayer film (flash-out time) was measured.

The results are also shown in Table 1 below.

Table 1 From the results shown in Table 1, it can be seen that the flush-out time of the embodiment of the present invention is about 20% shorter than that of the comparative example (conventional method).

In the above Examples and Comparative Examples, the flash-out time until the colored interlayer film becomes transparent was determined by n1.
The time required for the transparent interlayer film to become colored was also the same. Furthermore, in the case of converting to a different type of colored interlayer film, in the case of the present invention, compared to the conventional method, about 20%
% time reduction.

〔Effect of the invention〕

In the present invention, since the pigment ink composition is injected into the molten thermoplastic resin in the metering section of the extruder as described above, when changing the color of the interlayer film, at the start and end of film formation, It is no longer necessary to replace all of the resin in the production system, so the amount of unnecessary colored resin generated is significantly reduced compared to conventional technology, and the conversion time associated with color change can be significantly shortened. demonstrate.

tar support member, 27... ink discharge port, 28... filter, 29... holder, 30... spring,
31... Electromagnetic stirring drive device, 32... Electromagnetic stirring bar,
33...Ultrasonic generator.

Patent applicant Mitsubishi Monsanto Kasei Shiki Co., Ltd. Agent
Patent attorney Tsuyoshi Seibe

[Brief explanation of drawings]

FIG. 1 is a schematic configuration diagram of an extruder for carrying out the method of the present invention, FIG. 2 is a longitudinal cross-sectional view of an example of a pigment ink filter device used in the method of the present invention, and FIG. FIG. 2 is a cross-sectional view taken along line A-A in FIG. 2;

Claims (3)

[Claims] (1) A method for producing a colored interlayer film for laminated glass, which comprises adding a pigment ink composition consisting of a pigment and a plasticizer to a plasticized thermoplastic resin and extruding it into a sheet form from a T-die of an extruder. A method for producing a colored interlayer film for laminated glass, comprising injecting a pigment ink composition into a molten thermoplastic resin in a metering section of an extruder. (2) The method for producing a colored interlayer film for laminated glass according to claim (1), wherein the pigment ink composition is injected by a metering pump through a pigment ink filter device equipped with a means for preventing pigment sedimentation. (3) The pigment ink composition is composed of pigment particles and a plasticizer that can be blended with a thermoplastic resin, and the pigment particles have an average particle size of 2.5 μm or less and a 99% cumulative maximum particle size of 5.0 μm. The method for producing a colored interlayer film for laminated glass according to claim 1, wherein the pigment ink composition has an apparent pH of 4 to 10.