JPS6253464B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a laminated glass having metallic-colored characters, figures, symbols, etc. (hereinafter referred to as "metallic-colored patterns"). More specifically, it is a laminated glass that uses a film made of plasticized polyvinyl butyral as an interlayer film, has a beautiful metallic color pattern with no printing unevenness or bleeding, has a high light shielding rate in the pattern part, and has excellent adhesive properties. Regarding superior and durable laminated glass.

``Conventional technology'' Conventionally, in order to form metallic patterns such as gold or silver made of a strong coating film on a glass plate, the pattern formed with ceramic paint was baked onto the glass plate at a high temperature of several hundred degrees Celsius. I found a way.

However, such a method requires steps such as painting, drying, and baking, and furthermore, the portion where the pattern is baked has the disadvantage that the strength of the glass and the adhesive strength with the interlayer film are reduced. Furthermore, in order to form a gold or silver pattern, it was necessary to use gold (Au) powder and silver (Ag) powder as coloring agents, respectively, which caused economic problems. Furthermore, there is a known method of using metallic paint with a binder such as epoxy resin instead of ceramic paint, but in this case, a curing process is required, the strength of the paint film is weak, and the adhesion with the interlayer film is poor. It wasn't good.

In addition, laminated glass with a pattern added to the interlayer film in advance is a laminated glass with a resin interlayer between two glass plates on which characters or figures are displayed using ink.
13878) and a laminated glass (Japanese Patent Application Laid-Open No. 1983-65584) in which the intermediate film is a polyvinyl butyral film on which a printed image is formed by a transfer method.

However, none of the above-mentioned known laminated glasses are satisfactory; for example, when trying to make the pattern part have a high light shielding rate, the adhesive strength between the pattern part and the glass surface decreases, and at the same time, the pattern has uneven printing. On the other hand, if an attempt was made to make the adhesive strength between the pattern part and the glass surface high, there was a problem in that the pattern part would have a low light shielding rate.

``Problems to be solved by the invention'' The present invention can be manufactured at low cost without requiring complicated manufacturing processes or expensive pigments, has a high light shielding rate in the pattern area, has excellent adhesive properties, and has no problems such as uneven printing and bleeding. The purpose of the present invention is to provide a new laminated glass having a beautiful metallic color pattern and solving the problems of conventional products.

"Means for Solving the Problems" As a result of intensive research by the present inventors in order to overcome the drawbacks of the conventional laminated glass, such as a method of forming patterns on the interlayer film using ordinary paints, Polyvinyl butyral (hereinafter referred to as "PVB")
An interlayer film and this ink are prepared by dispersing metallic pigments in a solution dissolved in a mixed polar organic solvent consisting of esters and alcohols that has good permeability to PVB. The inventors have discovered that the above-mentioned problems can be solved by forming a pattern between the laminated glass plates, and have arrived at the present invention.

Therefore, the gist of the present invention is that in a laminated glass in which a film made of plasticized polyvinyl butyral is used as an interlayer film and glass plates are laminated on both sides of the interlayer film, there is a gap between the interlayer film and the glass plate. It has a metallic color pattern, and this metallic color pattern contains 10 to 20% by weight of polyvinyl butyral, 16 to 40% by weight of metallic color pigment, and dioctyl phthalate, dinonyl phthalate, dibutyl phthalate, butyl benzyl phthalate; dihexyl adipate, diheptyl adipate. ; Triethylene glycol bis(2-
at least one ester selected from the group consisting of ethyl butyrate), triethylene glycol dibenzoate, and tetraethylene glycol diheptanoate, and n-bentanol, n-hexanol, n-heptanol, n-octanol,
-Ethylhexanol and isomers thereof; and at least one alcohol selected from the group consisting of cyclohexanol and its monomethyl substituted product; and 40 to 75% by weight of a mixed polar organic solvent. It consists of laminated glass with a characteristic metallic color pattern.

The present invention will be explained in detail below.

In the present invention, the plasticized polyvinyl butyral serving as the base of the interlayer film for laminated glass is made from polyvinyl alcohol and a part of its hydroxyl groups are acetalized with butyraldehyde, and has a weight average molecular weight of about 20,000 to 300,000. degree of 50-95
% range of PVB as a base resin, and a plasticizer such as dioctyl phthalate, dibenzyl phthalate, dioctyl adipate, etc. is blended in an amount of about 10 to 50% by weight per 100 parts by weight of PVB.

In order to produce an interlayer film for laminated glass from the above-mentioned plasticized PVB, a sheet or film with a desired thickness may be formed by extrusion molding.

In the laminated glass according to the present invention, a metallic color pattern is formed between the laminated glass interlayer film made of the plasticized PVB and the glass plate laminated thereon. This metallic color pattern is produced using an ink consisting of a specific composition, namely, 10 to 20% by weight of polyvinyl butyral, 16 to 40% by weight of a metallic color pigment, and 40 to 75% by weight of a specific mixed polar organic solvent specified in the present invention. (hereinafter referred to as "PVB ink").

The PVB constituting the PVB ink includes ordinary PVB used in laminated glass interlayer films, adhesives, etc., that is, a weight average molecular weight of 300,000 or less, preferably 20,000 to 20,000.
A range of 10,000 is used. PVB in PVB ink
The content needs to be 10 to 20% by weight based on the PVB ink, and the type of metallic pigment used,
It is selected from within this range depending on the amount etc. If the PVB content is less than 10% by weight, the adhesion of the pattern will be insufficient, and if it is more than 20% by weight, the viscosity of the PVB ink will be extremely high, making it difficult to mix the metallic pigment uniformly. Inconveniences such as uneven printing are likely to occur.

Examples of the metallic pigments that make up PVB ink include copper-based golden pigments, aluminum-based silver pigments, and other inorganic pigments. It may be a mixture.

The metallic pigment content of the PVB ink is required to be 16 to 40% by weight based on the PVB ink.
If the content of metallic color pigment is less than 16% by weight, the light shielding rate of the pattern part will be low, and the desired beautiful metallic color pattern will not be formed.If the content is more than 40% by weight, the pattern part will be damaged. This results in insufficient adhesion.

The PVB ink used in the present invention is made by uniformly dispersing the PVB and metallic pigment in a specific mixed polar organic solvent specified below, and contains a high concentration of metallic pigment. Features.

The mixed polar organic solvents that make up PVB ink include:
Dioctyl phthalate, dinonyl phthalate, dibutyl phthalate, butylbenzyl phthalate;
Dihexyl adipate, diheptyl adipate;
At least one ester selected from the group consisting of triethylene glycol bis(2-ethylbutyrate), triethylene glycol dibenzoate, and tetraethylene glycol diheptanoate (hereinafter referred to as "esters"), and n-pentanol. , n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol and their isomers; at least one alcohol selected from the group consisting of cyclohexanol and its monomethyl substituted product (hereinafter referred to as "alcohols"). A mixed solvent consisting of is used.

In addition to acting as a medium for stably dispersing the metallic pigment, the esters work together with PVB in the PVB ink to provide the PVB ink with a function that does not deteriorate the viscoelastic properties of the interlayer film. In addition, the viscosity of the PVB ink can be adjusted by selecting the type and amount of alcohol added, which can prevent uneven printing that occurs when the viscosity is too high, and smearing of printed patterns that occurs when the viscosity is too low. It is effective in preventing

The mixing ratio of esters and alcohols is not particularly limited, and depends on the dispersion stability of the pigment,
The viscosity and printability can be determined on a case-by-case basis to optimize the viscosity and printability, but it is generally preferable to use a range of 0.8 to 2 parts by weight of the alcohol per 1 part by weight of the ester.

PVB ink composed of a mixed polar organic solvent made of the above specific combination maintains a good dispersion state even though it contains a high concentration of metallic pigment, and is suitable for printing patterns. It has a high viscosity, has excellent adhesion between the pattern part and the glass, and does not deteriorate the viscoelastic properties of the interlayer film.

Organic solvents other than the specific mixed polar organic solvents defined in the present invention, such as non-polar organic solvents,
If a metallic pattern is formed using an ink made of an organic solvent consisting of only one of esters and alcohols, the object of the present invention cannot be achieved. For example, in an ink using a non-polar organic solvent instead of the above-mentioned specific mixed polar organic solvent, dispersion and blending in this
PVB and metallic pigments cannot be dispersed stably and uniformly, so it is not possible to mix metallic pigments in high concentrations, and the pattern formed has uneven printing, resulting in poor light shielding rate and adhesive strength. This may cause other inconveniences.

The PVB ink used in the present invention can be produced by dispersing metallic pigments in esters in which PVB is dissolved and then mixing alcohols therein, or by dispersing metallic pigments in a mixture of PVB, esters, and alcohols. A roll mill, a ball mill, etc. can be used for these mixing and dispersing operations.

When forming a pattern, it can be done by hand with a paintbrush etc. in the case of single item or small quantity production, but in the case of mass production, it is possible to form the pattern on an uneven surface, for example, on the surface of an interlayer film with a satin finish. It is more preferable to carry out printing by a silk screen method or the like which can also print.

It is necessary to form the pattern between the interlayer film and the glass plate laminated thereon, but in the present invention, the pattern can be formed on either the interlayer film surface or the surface of the glass plate that is in contact with the interlayer film. Good too. When a pattern is formed on a glass surface, unlike when it is formed on an interlayer film, the pattern does not deform, and the PVB ink dries easily. However, when printing a pattern by a silk screen method or the like, it is easier to print on the interlayer film if the glass plate has a curved surface.

As the glass plate in the present invention, sheet glass, float glass, etc. can be used. Moreover, normal methods are used for manufacturing laminated glass.

"Effects of the Invention" The present invention has been described in detail above, and has the following particularly remarkable effects, and its industrial utility value is extremely large.

(1) The laminated glass with metallic color pattern according to the present invention is
Unlike the conventional ceramic paint baking method, it can be manufactured without using high temperatures and without making any particular changes to the ordinary laminated glass manufacturing process.
Since there is no need to use expensive gold powder, silver powder, etc., the pigment used can be manufactured at low cost.

(2) The laminated glass with metallic color pattern according to the present invention is
Since the applied metallic color pattern is formed using PVB ink with a specific composition, the pattern has a high light-shielding rate, and the pattern is beautiful without uneven printing or bleeding.

(3) The laminated glass with metallic color pattern according to the present invention is
The adhesive strength of the ink for forming metallic color patterns is strong, so even though the pattern area has a high light shielding rate,
It has excellent adhesion between the interlayer film surface and the glass plate surface laminated thereon, and has good durability.

"Examples" Next, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

Example 1 A solvent with a weight average molecular weight of triethylene glycol bis(2-ethyl butyrate) and cyclohexanol mixed at a weight ratio of 1:2 was added.
150000 PVB to 15% by weight to PVB ink
It was dissolved so that A copper-based golden pigment (Daikyo Kasei 7-LA, DOP content 40% by weight) dispersed in dioctyl phthalate (DOP) was added to this solution.
A golden PVB ink was prepared by stirring and mixing the PVB ink at a concentration of 40% by weight.

Next, using a 120-mesh silk screen, the pattern was printed on a 3 mm thick float glass surface with a square of 50 cm on each side. The printing thickness was 0.03 mm.

After drying for 10 minutes in a dryer heated to 70℃,
Using a 0.15 mm PVB film (Mitsubishi Monsanto Kasei/SAFLEX) as an interlayer film, preliminary pressure bonding was performed using the Niproller method, and then main pressure bonding was performed using the usual method to produce laminated glass with a golden pattern formed.

The light shielding rate of the patterned part of the obtained laminated glass is 100
%, and the adhesive strength was Pummeling value 4.5 at -18°C. We also tested the light resistance for 500 hours using a weatherometer.
No discoloration of the pattern was observed. Furthermore, no pattern bleeding or uneven printing was observed.

Example 2 After silk screen printing on PVB interlayer, 70
A patterned laminated glass was produced in the same manner as in Example 1, except that it was dried for 30 minutes at °C. The properties of the obtained laminated glass were similar to those obtained in Example 1. In other words, a light-shielding rate of 100%, a pummeling value of 4.5, and a 500-hour weatherometer light resistance test showed no discoloration. In addition, no pattern bleeding or uneven printing was observed.

Example 3 A solvent containing DOP and cyclohexanol mixed in a weight ratio of 1:2 has a weight average molecular weight of 150000.
Aluminum pigment (Dainichiseika Silver Al-500, DOP content 50% by weight) dispersed in DOP with 20% by weight of PVB dissolved in PVB ink.
Stir and mix 45% by weight of PVB ink to create a silver color.
A PVB ink was prepared.

Using this PVB ink, a patterned laminated glass was manufactured in the same manner as in Example 1. The light shielding rate of the patterned part of the obtained laminated glass is
100%, adhesive strength was 5.0 at -18°C, and a 500-hour light resistance test using a Weatherometer showed no discoloration of the pattern. Also, no uneven printing was observed.

Comparative Example 1 A golden PVB ink was prepared in the same manner as in Example 1 except that cyclohexanol was changed to cyclohexanone. Using this, a patterned laminated glass was produced in the same manner as in Example 1.

The light shielding rate of the patterned part of the obtained laminated glass is 75
% and adhesive strength decreased to -18°C Punmeling value 1.0, and uneven printing and pinholes were observed in the pattern area.

Comparative Example 2 A golden PVB ink was prepared in the same manner as in Example 1 except that cyclohexanol was replaced with acetone.

Using this, a patterned laminated glass was manufactured in the same manner as in Example 1.

The light shielding rate of the patterned part of the obtained laminated glass is 80
% and adhesive strength decreased to -18°C Punmeling value 2.0, and uneven printing and pinholes were observed in the pattern area.

Comparative Example 3 In the example described in Example 1, a gold patterned laminated glass was prepared in the same manner as in Example 1, except that the same type of pigment as in this example was used and the mixing amount was 75% by weight based on the total PVB ink. was manufactured.

The light shielding rate and light resistance were the same as those obtained in Example 1, but the adhesive strength was reduced to a punch ring value of 2 at -18°C.

Comparative Example 4 A laminated glass with a golden pattern was produced in the same manner as in Example 1, except that the same type of pigment as in this example was used and the amount mixed was 10% by weight.

The pattern area of the resulting laminated glass has a light shielding rate of 87%.
The adhesive strength was -18°C Punmeling value 5.5. The light resistance was similar to that obtained in Example 1.

Claims (1)

[Claims] 1 In a laminated glass in which a film made of plasticized polyvinyl butyral is used as an interlayer film and glass plates are laminated on both sides of the interlayer film, a metallic color pattern is provided between the interlayer film and the glass plate, and the metallic color pattern is formed between the interlayer film and the glass plate. 10-20% by weight of polyvinyl butyral, 16% of metallic color pigment
~40% by weight, as well as dioctyl phthalate, dinonyl phthalate, dibutyl phthalate, butylbenzyl phthalate; dihexyl adipate, diheptyl adipate; triethylene glycol bis(2-ethyl butyrate), triethylene glycol dibenzoate, tetraethylene glycol dihepta at least one ester selected from the group consisting of noate; n-pentanol, n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol and isomers thereof; cyclohexanol and its monomethyl substituted product; A laminated glass with a metallic color pattern, characterized in that it is formed with an ink comprising 40 to 75% by weight of a mixed polar organic solvent and at least one alcohol selected from the group consisting of: