JP2000256433A - Benzoguanamine resin composition, preparation thereof, and fluorescence conversion film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a benzoguanamine resin composition superior in heat resistance and a reduced in cure shrinkage, and a fluorescence conversion film which is free from generation of deformations or pinholes by cure shrinkage during preparation and excellent in fluorescence conversion efficiency. SOLUTION: The benzoguanamine resin composition having a glass transition temperature of from 80 to 150 deg.C is obtained by mixing a reaction product of an aromatic sulfonamide and formalin with a reaction product of a benzoguanamine and formalin and then polymerizing the resultant mixture by heating. The fluorescence conversion film is prepared by dispersing a fluorescent pigment in the resin composition to prepare a composition and then forming a film from the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a benzoguanamine resin composition having high utility as a binder resin for a fluorescence conversion film, a method for producing the same, and a fluorescence conversion film using the benzoguanamine resin composition as a binder resin.

[0002]

2. Description of the Related Art An organic electroluminescent device utilizing electroluminescence has high visibility due to self-emission, and is a completely solid-state device. Therefore, it is easy to reduce the weight and thickness of the device. Since it can be driven by voltage, it is expected as a light emitting element in a display.

As described above, the organic electroluminescence element has excellent performance, but there are still problems to be solved in order to realize a full-color display. Has been made. For example, Japanese Patent Application Laid-Open No. 57-157487 proposes a method of arranging electroluminescent materials emitting light in three primary colors in a matrix. In this case, it is difficult to perform wet patterning of the organic electroluminescent material. There is a disadvantage.

In view of the above, Japanese Patent Application Laid-Open No.
Japanese Patent Publication No. 88 proposes a method of extracting three primary colors by combining an electroluminescent element emitting white light and a color filter. By the way, in this case, there is a disadvantage that the obtained luminance of each color is significantly attenuated as compared with the luminance of the white light source. Further, Japanese Patent Laid-Open No. 3-1
Japanese Patent Application No. 52897 proposes a method of using a blue light emitting electroluminescent element as a light source and obtaining green or red light emission by fluorescence conversion of a dye excited by the blue light emitting element. In this case, the method is superior in that the luminance is less attenuated than when a color filter is used, but there is a disadvantage that the conversion efficiency of the fluorescence conversion film is not sufficient.

Therefore, there is a demand for the development of a fluorescence conversion film having excellent conversion efficiency and a material constituting the film.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a benzoguanamine resin composition having high heat resistance, a method for producing the same, and a fluorescence conversion film using the benzoguanamine resin composition as a binder resin and having excellent conversion efficiency. It is intended for.

[0007]

The present inventors have conducted various studies to achieve the above object, and as a result, the benzoguanamine resin composition which has been used as a binder resin of the conventional fluorescence conversion film has a glass transition. The temperature was as low as 60 to 70 ° C. and the heat resistance was insufficient, so that excessive shrinkage and pinholes were generated at the time of heat curing after film formation, and the performance of the fluorescence conversion film was reduced. The glass transition temperature is improved from 80 to 150 by improving the production method of the resin composition.
It has been found that the above object can be achieved by obtaining a benzoguanamine resin composition at a temperature of ° C. and using this as a binder resin for a fluorescence conversion film, and based on these findings, the present invention has been completed.

That is, the gist of the present invention is as follows. (1) A benzoguanamine resin composition having a glass transition temperature of 80 to 150 ° C. obtained by mixing a reaction product (A) of an aromatic sulfonamide and formalin and a reaction product (B) of a benzoguanamine and formalin and heating and polymerizing the mixture. object. (2) The benzoguanamine resin composition according to the above (1), wherein the reaction product (B) contains at least 60% by weight of various methylols of bezoguanamines. (3) A reaction product of aromatic sulfonamide and formalin (A), and a reaction product of benzoguanamines and formalin (B) are mixed and heated and polymerized.
A method for producing a benzoguanamine resin composition at 150 ° C. (4) A reaction product (A) of an aromatic sulfonamide and formalin is mixed with a reaction product (B) containing 60% by weight or more of various methylols of benzoguanamines obtained by a reaction between benzoguanamines and formalin. A method for producing a benzoguanamine resin composition having a glass transition temperature of 80 to 150 ° C., which is subjected to heat polymerization. (5) A fluorescence conversion film formed by forming a composition in which a fluorescent dye is dispersed in the benzoguanamine resin composition according to (1) or (2).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The benzoguanamine resin composition of the present invention is obtained by mixing a reaction product (A) of an aromatic sulfonamide with formalin and a reaction product (B) of a benzoguanamine and formalin, followed by heat polymerization. Is a benzoguanamine resin composition having a glass transition temperature of 80 to 150 ° C.

The aromatic sulfonamide used as a raw material for producing the benzoguanamine resin composition of the present invention may be benzenesulfonamide, o-toluenesulfonamide, p-toluenesulfonamide or any of these in any proportion. Mixtures are mentioned as suitable. Examples of the benzoguanamine used as a raw material include those having a lower alkyl group as a substituent, such as benzoguanamine, 4-methylbenzoguanamine, and 4-tert-butylbenzoguanamine.

Next, in the method for producing the benzoguanamine resin composition of the present invention, first, an aromatic sulfonamide is reacted with formalin to obtain a reaction product (A).
The reaction conditions in this case are slightly different depending on the type of the raw materials, but the molar ratio of the raw materials used is aromatic sulfonamide: formalin = 1: 0.8 to 2, preferably aromatic sulfonamide: Formalin = 1: 1 to 1.
2, and the reaction temperature is 90 to 120 ° C, preferably 90 to 120 ° C.
100 ° C., the reaction time is 0.5 to 2 hours, preferably 1 to 2 hours.
2 hours. In this reaction, the amide group in the aromatic sulfonamide is methylolated by formalin.
If the temperature is lower than ℃, this reaction may not proceed sufficiently.

The atmosphere for carrying out this reaction may be air, nitrogen gas, argon gas or the like, but nitrogen gas is preferred. During the reaction period, it is preferable to stir moderately, and the stirring speed is 100 to 10
00 rpm, preferably 300 to 800 rpm.
Next, the reaction for obtaining the reaction product (B) by the reaction between the benzoguanamines and formalin is slightly different depending on the type of the benzoguanamines used, but the feed ratio of the raw materials is benzoguanamine: formalin = 1: 1 to 3, preferably benzoguanamines: formalin = 1: 1.8 to 2.2, reaction temperature 80 to 120 ° C, preferably 90 to 110 ° C, reaction time 0.5 to 2 hours, Preferably, it is 1-2 hours. The atmosphere for performing this reaction is air,
Any gas such as nitrogen gas or argon gas may be used, but nitrogen gas is preferable. During the reaction period, it is preferable to stir moderately, and the stirring speed is 300 to 300 when the viscosity is low.
800 rpm, 50-100 rpm when viscosity is high
It is preferable that

In this reaction, one or both of the two amino groups in the benzoguanamines are converted into methylol by formalin. In the reaction product (B), various methylols, ie, monomethylols , The total amount of the dimethylol form and the trimethylol form is 6 in the intensity ratio in the mass spectrum analysis.
It is desirable to prepare so as to have a value of 0% or more. The benzoguanamine resin composition obtained by reacting the reaction product (B) thus prepared with the reaction product (A) has a narrow molecular weight distribution and a high glass transition temperature, and has a high heat resistance. This is preferable because it provides excellent solubility in a solvent and excellent solubility in a solvent.

Next, regarding the reaction between the reaction product (A) and the reaction product (B), the reaction product (A): reaction product (B) =
0.1: 0.9 to 0.5: 0.5, preferably reaction product (A): reaction product (B) = 0.25: 0.75
0.35: 0.65 is convenient. here,
When the charging ratio of the reaction product (A) is less than 0.1, the glass transition temperature of the obtained benzoguanamine resin composition may decrease, and the charging ratio of the reaction product (A) may be 0.5. This is because, if the ratio exceeds 3, cracks may occur when a film is formed using the obtained benzoguanamine resin composition and cured by heating.

The reaction between the reaction product (A) and the reaction product (B) is preferably carried out in a two-stage reaction of preliminary polymerization and main polymerization, but may be carried out in a single-stage polymerization reaction. . In the prepolymerization here, the reaction temperature is 80 to 1
The reaction may be performed at 20 ° C, preferably 80 to 100 ° C, for a reaction time of 0.5 to 1 hour. The atmosphere in this case may be air, nitrogen gas, argon gas, etc.
The stirring speed during the reaction is 200 to 700 rpm, preferably 300 to 500 rpm.

Next, the main polymerization reaction between the reaction product (A) and the reaction product (B) is carried out at a reaction temperature of 120 to 160.
C., preferably at 130-140.degree.
The reaction may be carried out for up to 5 hours, preferably for 2 to 3 hours. The atmosphere in this case is preferably air, nitrogen gas, argon gas, or the like. When the reaction between the reaction product (A) and the reaction product (B) is carried out in a single-stage polymerization reaction, the reaction temperature is set to 140 to 100 with stirring following the preliminary polymerization reaction.
The reaction may be performed by raising the temperature to 160 ° C. and under a nitrogen gas flow for 1 to 3 hours. Water generated by this reaction may be removed by a Dean-Stark apparatus or the like.

Next, the fluorescence conversion film of the present invention can be obtained by forming a dye-containing resin composition in which a dye is dispersed in the benzoguanamine resin composition obtained as described above, and then curing the film. Suitable dyes used for the fluorescence conversion film include coumarin dyes, xanthene dyes such as rhodamine B and rhodamine 6G, cyanine dyes, oxazine dyes, and naphthalimide dyes.

Next, the method of producing the fluorescence conversion film of the present invention may be a method of forming a dye-containing resin composition in which the above dye is dispersed in a benzoguanamine resin composition on a light-transmitting substrate. . In this case, the content ratio of the pigment dispersed in the benzoguanamine resin composition is usually 0.01 to 1
0% by weight, preferably 0.1 to 5% by weight. Also,
The film forming method in this case is not particularly limited, and a normal spin coating method, a coating method, a printing method, or the like may be employed. Among them, the spin coating method is particularly preferable. As the solvent used in this case, various solvents can be used, but ethylene glycol ether solvents such as ethylene glycol monoethyl ether and ethylene glycol monomethyl ether, ethylene glycol ester solvents such as ethylene glycol monoethyl ether acetate, 2-acetoxy-1-methoxypropane, 1-acetoxy-2-ethoxypropane, cyclohexanone and the like can be used. Among these,
Ethylene glycol ether solvents such as ethylene glycol monoethyl ether and ethylene glycol monomethyl ether are particularly preferred.

The thickness of the thus-formed fluorescent conversion film must be a film thickness necessary for converting the incident light into a desired wavelength in the fluorescent conversion film.
The film thickness may be appropriately selected in the range of usually 1 to 100 μm, preferably 1 to 20 μm. Further, as the light-transmitting substrate used at the time of forming the fluorescence conversion film, a substrate having a smooth transmittance of 50% or more in the visible light region having a wavelength of 400 to 700 nm and a smooth substrate is preferable. As such a translucent substrate, for example,
A glass substrate or a synthetic resin plate is used. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminum silicate glass, borosilicate glass, barium borosilicate glass, and quartz. Further, as the synthetic resin plate, polycarbonate resin, acrylic resin, polyethylene terephthalate resin,
Polyether sulfide resin, polysulfone resin and the like can be mentioned.

This fluorescence conversion film can be used for various light sources, for example, L
EDs, cold cathode tubes, organic electroluminescent devices,
It can be used in combination with an inorganic electroluminescent element, a fluorescent lamp, an incandescent lamp, etc. Among them, it is particularly useful when a display using an organic electroluminescent element is made full-color. And
In order to further improve the quality of the light transmitted through the fluorescence conversion film, another color filter for converting the light to a desired wavelength is provided in parallel and the color purity is adjusted, whereby higher definition can be achieved. Examples of the color filters provided here include perylene pigments, lake pigments, azo pigments, quinacridone pigments, anthraquinone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, A color filter using only one type of phenylmethane-based basic dye, indanthrone-based pigment, indophenol-based pigment, cyanine-based pigment, dioxazine-based pigment, or a mixture of two or more types, or a color filter using these dyes Dissolved in a binder resin to form a color filter.

Next, as a mode of using this fluorescence conversion film, there is the following configuration. (1) Light source / fluorescence conversion film (2) Light source / translucent substrate / fluorescence conversion film (3) Light source / fluorescence conversion film / light transmission substrate (4) Light source / light transmission substrate / fluorescence conversion film / light transmission (5) Light source / fluorescent conversion film / color filter (6) Light source / translucent substrate / fluorescent conversion film / color filter (7) Light source / fluorescent conversion film / translucent substrate / color filter (8) light source / (9) Light source / Transparent substrate / Fluorescent conversion film / Color filter / Transparent substrate (10) Light source / Fluorescent conversion film / Color filter / Transparent Optical Substrate The configuration exemplified here may be created by sequentially laminating individual components, or may be created by lamination.

[0022]

[Example 1]

(1) Reaction between aromatic sulfonamide and formalin In a reaction vessel having an internal volume of 100 ml, 25.7 g of p-toluenesulfonamide as aromatic sulfonamide was added.
And 4.5 g of paraformaldehyde, and the air in the flask was replaced with nitrogen gas for 30 minutes while stirring at room temperature at 50 rpm. Then, while keeping the nitrogen gas seal, the rotation speed was increased to 200 rpm, and
The reaction solution was heated in a hot water bath at ℃. And the reaction solution is 8
At about 0 ° C., when a part of the reactants was melted and became a suspended state, the number of revolutions was increased to 720 rpm, and heating and stirring were continued for another 15 minutes. After the temperature of the reaction solution reached 100 ° C., the reaction was further performed at this temperature for 1 hour. After the completion of the reaction, the mixture was left to cool, and 27.8 g of a solid reaction product (A) was obtained.
I got This solid was pulverized with a mortar into powder.

(2) Reaction of Benzoguanamine and Formalin 56.2 g of benzoguanamine and 18.0 g of paraformaldehyde were placed in a reaction vessel having an internal volume of 200 ml, and stirred at room temperature at a rotation speed of 50 rpm.
The air in the flask was replaced with nitrogen gas for 0 minutes. Then, while kneading with a nitrogen gas seal, 110 ° C.
The reaction was heated in a hot water bath for 55 minutes.
When the temperature of the reactant reaches 100 ° C.,
The reaction was carried out under stirring at 150 rpm for 2 hours to obtain a white viscous liquid. After the completion of the reaction, the reaction solution was allowed to cool to obtain 72.3 g of a solid reaction product (B). This solid was pulverized with a mortar into powder. Using this powder, the reaction product (B) was subjected to mass spectrometry. As a result, in the intensity ratio, the monomethylol form of benzoguanamine was 28%, the dimethylol form was 34%, and the trimethylol form was 9%. The total content of each methylol form of benzoguanamine was 71%.

(3) Pre-polymerization of reaction product (A) and reaction product (B) 27.3 g of powder of reaction product (A) obtained in (1) above
And powder 71.1 of the reaction product (B) obtained in (2) above.
g, and the mixture was charged into a reaction vessel and replaced with nitrogen gas for 30 minutes while stirring at a rotation speed of 90 rpm. Then, 110 ° C. while stirring with the nitrogen gas sealed.
Heated in an oil bath. When the temperature inside the reaction vessel is 90
When the temperature reached ° C., the raw material powder began to melt, and thus the heating was continued at a rotation speed of the stirring blade of 250 rpm. After the temperature in the reaction vessel reached 100 ° C., the temperature was kept at this temperature for 1 hour to carry out the reaction. As the reaction proceeds, the viscosity of the reaction product increases, so that the rotation speed of the stirring blade is gradually reduced to 120 rpm immediately before the end of the reaction. In this way,
A white viscous liquid was obtained. After the completion of the reaction, the mixture was allowed to cool to obtain 97 g of a solid prepolymerized product. This solid was pulverized with a mortar into powder.

(4) Main polymerization of the reaction product (A) and the reaction product (B) The reduced pressure dryer was heated, and suction was performed with an aspirator with the leak valve opened, thereby forming a normal pressure flow system. After adjusting the temperature in the dryer to 130 ° C., a porcelain dish containing 97 g of the prepolymer powder obtained in the above (3) was carried into the dryer, and kept at 130 ° C. for 3 hours. Reacted.

After completion of the reaction, the porcelain dish was taken out of the dryer and allowed to cool, and the reaction product in the porcelain dish was ground as it was with a porcelain pestle. The yield of the benzoguanamine resin composition obtained here was 91.2 g. The glass transition temperature of this benzoguanamine resin composition was 102 ° C. The average molecular weight of this benzoguanamine resin composition was about 1,000 as measured by GPC. Further, the molecular weight distribution of the benzoguanamine resin composition was narrow and uniform as shown in FIG. The solubility of the benzoguanamine resin composition in a solvent was excellent in ethylene glycol monoethyl ether and ethylene glycol monoethyl ether acetate.

Example 2 (1) Reaction of Aromatic Sulfonamide with Formalin A reaction product (A) powder was obtained in the same manner as in Example 1 (1). (2) Reaction of benzoguanamine with formalin A powder of the reaction product (B) was obtained in the same manner as in (2) of Example 1. (3) Polymerization of reaction product (A) and reaction product (B) 27.3 g of powder of reaction product (A) obtained in (1) above
And powder 71.1 of the reaction product (B) obtained in (2) above.
After mixing, the mixture was charged into a reactor equipped with a stirrer equipped with a nitrogen gas blowing port and a Dean Starck device, and replaced with nitrogen gas for 30 minutes while stirring at a rotation speed of 90 rpm.

Then, the mixture was heated in a 110 ° C. oil bath with stirring while keeping the nitrogen gas sealed. When the temperature in the reactor reached 90 ° C., the raw material powder began to melt, so the heating was continued with the rotation speed of the stirring blade at 250 rpm. After the temperature in the reactor reached 100 ° C., the reaction was maintained at this temperature for 1 hour. As this reaction progresses,
Since the viscosity of the reaction product increased, the rotation speed of the stirring blade was gradually lowered, and the rotation speed was set to 120 rpm. Then, the reaction product became a white viscous liquid.

Subsequently, the temperature of the oil bath was set to 160 ° C.
And the temperature in the reactor is increased to 140 to 15 with stirring.
The reaction was maintained for 2 hours at a temperature of 0 ° C. After completion of the reaction, the reaction product was taken out of the reactor, placed in a porcelain dish, and ground with a porcelain pestle. The yield of the benzoguanamine resin composition obtained here was 88.3 g.

The benzoguanamine resin composition had a glass transition temperature of 110 ° C. The average molecular weight of this benzoguanamine resin composition was about 1,100 as measured by GPC. Further, the molecular weight distribution of the benzoguanamine resin composition was narrow and uniform as shown in FIG. 1B. The solubility of the benzoguanamine resin composition in a solvent was excellent in ethylene glycol monoethyl ether and ethylene glycol monoethyl ether acetate.

Example 3 (1) Reaction of Aromatic Sulfonamide with Formalin A reaction product (A) powder was obtained in the same manner as in Example 1 (1). (2) Reaction of benzoguanamine with formalin A powder of the reaction product (B) was obtained in the same manner as in (2) of Example 1. (3) Production of benzoguanamine resin composition containing pigment 27.3 g of powder of reaction product (A) obtained in (1) above
And powder 71.1 of the reaction product (B) obtained in (2) above.
g, and 1 g of coumarin 6 as a pigment,
The same operation as (3) and (4) of Example 1 was performed. However, the temperature in the dryer during the main polymerization was 150 ° C., and the reaction time was 2 hours. The solid obtained by this reaction was pulverized to obtain 92.3 g of a yellow powder. The glass transition temperature of the benzoguanamine resin composition containing the pigment obtained here was 115 ° C. The solubility of this resin composition in ethylene glycol monoethyl ether and ethylene glycol monoethyl ether acetate was all good.

Example 4 10 g of a benzoguanamine resin composition containing the pigment obtained in (3) of Example 3 above
With ethylene glycol monoethyl ether 10 as a solvent.
g and dissolved. Then, under stirring, 20 parts of poly (4-vinylpyridine) was added as an etching resin.
A 50% by weight ethylene glycol monoethyl ether solution (50 g) was added and stirred to obtain a clear yellow solution. Using this yellow solution, a film was formed on a glass substrate by spin coating to obtain a uniform yellow fluorescence conversion film. The performance of the obtained fluorescence conversion film was evaluated based on the conversion efficiency when blue light was converted to green light. As a result, the ratio of the brightness (nit) of the green light to the brightness (nit) of the blue light was 93%. Next, the obtained fluorescence conversion film was placed in an electric oven maintained at 160 ° C. for 1 hour.
It was charged for a time and the heat resistance was evaluated. As a result, the thickness of the fluorescence conversion film before receiving the thermal history was 13.8 μm, but slightly changed to 13.7 μm after receiving the thermal history. Further, the state of the fluorescence conversion film after receiving the thermal history did not change compared to before the thermal history.

Example 5 The fluorescence conversion film obtained in the same manner as in Example 4 was placed in an electric oven maintained at 160 ° C. for 2 hours, and the heat resistance was evaluated. As a result, the thickness of the fluorescence conversion film before receiving the thermal history was 14.2 μm.
m was 14.1 μm after receiving the thermal history
Had changed slightly. Further, the state of the fluorescence conversion film after receiving the thermal history did not change compared to before the thermal history.

Comparative Example 1 (1) Reaction of Aromatic Sulfonamide with Benzoguanamine and Formalin In a reaction vessel having an internal volume of 200 ml, 25.7 g of p-toluenesulfonamide was used as an aromatic sulfonamide.
And 4.5 g of paraformaldehyde and a rotation speed of 50
While stirring at rpm, the air in the flask was replaced with nitrogen gas for 30 minutes at room temperature. Then, while keeping the nitrogen gas seal, the rotation speed was increased to 200 rpm, and
The reaction was heated in a 0 ° C. water bath. Then, when the reaction liquid was around 80 ° C. and a part of the reactants was melted and became a suspended state, the rotation speed was increased to 720 rpm, and heating and stirring were continued for another 15 minutes. Reaction temperature is 100 ° C
After that, the reaction was further performed at this temperature for 1 hour.

Then, a mixture of 56.2 g of benzoguanamine and 18.0 g of paraformaldehyde was added little by little to the reaction solution, and the air in the flask was replaced with nitrogen gas at room temperature for 30 minutes while stirring at a rotation speed of 50 rpm. did. Next, the reaction solution was heated in a hot water bath at 110 ° C. for 1 hour while kneading with the nitrogen gas sealed. When the temperature of the reaction solution reached 100 ° C, the reaction was allowed to proceed for 2 hours with stirring at a rotation speed in the range of 100 to 150 rpm to obtain a white viscous liquid. After the completion of the reaction, the reaction solution was allowed to cool to obtain 100.3 g of a solid reaction product. The obtained solid was pulverized with a mortar into powder.

(2) Polymerization reaction The vacuum dryer was heated, and suction was carried out with an aspirator with the leak valve opened to form a normal pressure flow system. Next, after adjusting the temperature in the dryer to 130 ° C., the above (1)
A porcelain dish containing 100 g of the reaction product powder obtained in the above was placed in the dryer and reacted at 130 ° C. for 3 hours. After the completion of the reaction, the porcelain dish was taken out of the dryer and allowed to cool, and the reaction product in the porcelain dish was directly ground with a porcelain pestle. The yield of the benzoguanamine resin composition obtained here was 93 g.

The glass transition temperature of this benzoguanamine resin composition was 60 ° C. The average molecular weight of this benzoguanamine resin composition was about 800 as measured by GPC, and the molecular weight distribution was somewhat broad and irregular as shown in FIG. 2C. Further, the solubility of this benzoguanamine resin composition in a solvent was excellent in ethylene glycol monoethyl ether and ethylene glycol monoethyl ether acetate.

Comparative Example 2 A benzoguanamine resin composition was obtained in the same manner as in Comparative Example 1, except that the temperature in the dryer during the polymerization reaction was 150 ° C., and the polymerization time was 3 hours.
As shown in FIG. 2D, the molecular weight distribution of the benzoguanamine resin composition obtained here was larger than that obtained in Comparative Example 1, and had a wide and uneven distribution. And regarding the solubility of this benzoguanamine resin composition in the solvent, ethylene glycol monoethyl ether, poor solubility in any of ethylene glycol monoethyl ether acetate,
It became cloudy.

Comparative Example 3 The procedure of Comparative Example 1 was repeated except that 56.2 g of benzoguanamine, 18.0 g of paraformaldehyde and 1 g of coumarin 6 were used as raw materials.
A benzoguanamine resin composition was obtained. The glass transition temperature of the benzoguanamine resin composition obtained here was 62 ° C.
Met.

Comparative Example 4 A fluorescent conversion film was obtained in the same manner as in Example 4 except that the benzoguanamine resin composition containing the pigment obtained in Comparative Example 3 was used. The conversion efficiency of the thus obtained fluorescence conversion film was 92%. Next, this fluorescence conversion film was placed in an electric oven maintained at 160 ° C. for 1 hour, and heat resistance was evaluated. as a result,
The thickness of the fluorescence conversion film before receiving the thermal history was 13.6 μm, but after receiving the thermal history, a slight change was observed at 13.4 μm. Further, in the state of the fluorescence conversion film after receiving the heat history, small spots that did not exist before receiving the heat history were observed on the entire surface of the film.

Comparative Example 5 Evaluation of the heat resistance of the fluorescence conversion film obtained in the same manner as in Comparative Example 4 was performed in the same manner as in Comparative Example 4 except that the holding time at 160 ° C. was changed to 2 hours. .
As a result, the thickness of the fluorescence conversion film before receiving the thermal history is 1
What was 4.3 μm, after receiving the thermal history,
It had changed significantly to 3.8 μm. Further, in the state of the fluorescence conversion film after receiving the heat history, generation of a large number of holes on the film surface was recognized.

[0042]

As described above, the benzoguanamine resin composition of the present invention has a high glass transition temperature, excellent heat resistance, and excellent solubility in a solvent used for etching by photolithography. It is highly useful as a material in which a dye is dispersed and used for forming a fluorescence conversion film. Further, the fluorescence conversion film of the present invention has high conversion efficiency and excellent heat resistance.

[Brief description of the drawings]

FIG. 1 is a graph showing the molecular weight distribution of the benzoguanamine resin compositions obtained in Examples 1 and 2.

FIG. 2 is a graph showing the molecular weight distribution of the benzoguanamine resin compositions obtained in Comparative Examples 1 and 2.

Claims (5)

[Claims] 1. A reaction product of an aromatic sulfonamide and formalin (A), and a reaction product of a benzoguanamine and formalin (B) are mixed and heated to obtain a glass transition temperature of 80 to 150 ° C. Benzoguanamine resin composition. 2. The benzoguanamine resin composition according to claim 1, wherein the reaction product (B) contains not less than 60% by weight of various methylols of bezoguanamines. 3. A benzoguanamine resin composition having a glass transition temperature of 80 to 150 ° C., wherein a reaction product (A) of an aromatic sulfonamide and formalin and a reaction product (B) of a benzoguanamine and formalin are mixed and heated and polymerized. Manufacturing method. 4. A reaction product (A) of an aromatic sulfonamide and formalin, and a reaction product (B) containing 60% by weight or more of various methylols of benzoguanamines obtained by the reaction of benzoguanamines and formalin. A method for producing a benzoguanamine resin composition having a glass transition temperature of 80 to 150 ° C. to be mixed and polymerized by heating. 5. A fluorescence conversion film obtained by forming a composition in which a fluorescent dye is dispersed in the benzoguanamine resin composition according to claim 1 or 2.