JPH07333034A - Apparatus and method for measuring cure shrinkage - Google Patents

Abstract

PURPOSE:To bring an easy and highly accurate measurement method into actual use at the time of measuring a cure shrinkage of synthetic resin. CONSTITUTION:Sample comprising liquid resin which has been weighed is put into a sealed container 1, and after the sealed container 1 and a standard container 2 are connected to a pressure gauge 3 using a pipe 4 and held at a standard temperature, hardening energy is applied from an energy supply source 5 to the sealed container 1 and the standard container 2 to harden the liquid resin in the sealed container 1. Then after the sealed container 1 and the standard container 2 are returned to the standard temperature and difference in pressure between both containers is measured by the pressure gauge 3, its ratio to the weighed amount of the liquid resin is taken to measure a cure shrinkage.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for measuring the cure shrinkage of a resin. A resin mold is generally used for the exterior of electronic parts, and a synthetic resin is also used as an insulating layer of a multilayer circuit board, similar to an inorganic insulator.

That is, since the life of electronic parts is often affected by humidity, for highly reliable parts, a hermetic seal using glass terminals and a metal case is used.
Although packages were used, resin mold packages have come to be used in a wide range of fields due to improvements in resin materials, and spin coating is used for resins as insulating layers for semiconductor integrated circuits and multilayer circuit boards. It is used as a material for forming an interlayer insulating layer because it can be applied and the surface of a substrate can be easily flattened.

Here, in order to form a pattern with high dimensional accuracy, it is necessary to grasp the curing shrinkage ratio of the resin, and the user of the synthetic resin designs the pattern using the values published by the material manufacturer. In some cases, it may be necessary to use the raw material resin synthesized in-house, or it may be desirable to use it under conditions different from the conditions specified by the material manufacturer.

For example, when it is necessary to change the type of the polymerization accelerator and use it at a lower temperature, the user himself has to measure the cure shrinkage of the resin.

[0005]

2. Description of the Related Art The cure shrinkage of a resin has been calculated from the change in the specific gravity of the material used before and after the curing treatment.

That is, the specific gravity (d) is obtained by measuring the volume and weight of a material in a liquid state before being cured, and then the material is cured while being thinly applied to a substrate. When the specific gravity (d ') is obtained by peeling and measuring the volume, 1-d / d' is the shrinkage rate.

[0007]

Conventionally, the shrinkage ratio has been measured using such a method. However, the resin has a high viscosity before being cured,
It is difficult to determine the volume accurately, and it is necessary to use a large amount of resin to make this possible. It is difficult to accurately determine the specific gravity of a cured resin that is obtained in the form of a thin film, and it is often necessary to use a complicated method such as a floatation method. Although the sample before curing often contains an organic solvent, the accuracy cannot be improved in the conventional method because it is regarded as the resin before curing and measured. There was such a problem, and improvement was necessary.

[0008]

[Means for Solving the Problems] The above-mentioned problems include an airtight container for accommodating a measurement sample and transmitting ultraviolet rays, a standard container of the same material and size as the airtight container, and a pressure gauge for measuring changes in atmospheric pressure. , A pipe connecting a closed container and a standard container to a pressure gauge, and at least an energy supply source for applying curing energy to a measurement sample contained in the closed container,
While connecting the closed container and the standard container to the pressure gauge by piping, using a curing shrinkage rate measuring device formed to uniformly apply light energy or heat energy to the closed container and the standard container, Put a sample of liquid resin weighed into a closed container, connect this closed container and standard container to a pressure gauge using a pipe and maintain at standard temperature, then cure this closed container and standard container from an energy source. After energy is applied to cure the liquid resin in the closed container, the closed container and the standard container are returned to the standard temperature, the pressure difference between them is measured with a pressure gauge, and the following (1) formula is used. Obtain the volume change of the resin.

ΔV = VΔP / (P−ΔP) (1) where ΔV is the volume change of the resin, V is the volume of the closed container, P is the pressure in the closed container, and ΔP is the pressure drop amount.ゝ, this value (ΔV) and the volume of the original liquid resin (v)
The ratio (ΔV / v) is the curing shrinkage rate of the resin.

[0010]

In the present invention, when the resin is cured in a closed container and the resin contracts due to the curing, the inside of the container is depressurized, and thus the curing shrinkage ratio of the resin is obtained.

1 and 2 show the constitution of a curing shrinkage measuring device according to the present invention. FIG. 1 is applied to an ultraviolet curable resin, and FIG. 2 is applied to a heat curable resin. Therefore, they differ only in the curing energy source.

That is, the apparatus according to the present invention comprises an airtight container 1 having the same capacity, a standard container 2, a pressure gauge 3 and a pipe 4 connecting them, and is hermetically formed by a sliding structure using glass or the like. ing.

When the ultraviolet ray 6 is used as the energy source 5 required for curing the resin, the closed container 1 and the standard container 2 must be made of a material such as quartz or glass that allows the ultraviolet ray to pass therethrough. A high pressure mercury lamp or the like is used as. Further, as shown in FIG. 2, a heater is used as the energy supply source 5 for the thermosetting resin, but in any case, it is necessary to heat the closed container 1 and the standard container 2 evenly.

According to the present invention, assuming that the pressure in the closed container is P and the volume of the closed container is V, if the volume of the resin decreases by ΔV due to hardening of the resin, the volume of the atmosphere in the container changes by ΔV.
Since it increases by V and causes a pressure drop of ΔP, the relation of PV = (P−ΔP) (V + ΔV) (2) is established according to Boyle's law, and the following (3) The amount of change in volume of the resin due to curing can be calculated by the equation).

ΔV = VΔP / (P−ΔP) (3) Then, the volume (v) of the original liquid resin previously weighed.
The ratio (ΔV / v) is the cure shrinkage of the resin.

Next, regarding the sensitivity of the measuring device according to the present invention, when using, for example, water as the measuring medium of the pressure gauge, 1 atm corresponds to 10.3 m of the water column.
Corresponds to 0.0001 atm.

Now, assuming that the closed container has a volume of 20 cc,
From the formula (3), the pressure difference of 1 mm of water column is ΔV = 0.0018cc, which corresponds to the volume change of 0.0018cc. Therefore, assuming that a pressure difference of 1 mm of water is generated by curing 0.2 cc of liquid resin, the cure shrinkage can be measured with a sensitivity of about 1%.

In the present invention, it is necessary to measure the volume of the sample before curing in order to calculate the shrinkage ratio, which is a problem of the conventional method, that is, it is difficult to accurately measure the volume before curing. The problem is not completely solved.

However, the influence of the measurement error on the measurement accuracy of the shrinkage rate is much smaller. Whereas in the conventional method, the volume change is obtained from the difference between the volume before curing and the volume after curing,
This is because the volume change is directly obtained as an absolute value in the present invention.

Next, when curing the resin, when the raw material contains a material such as a solvent which is easily vaporized by heating, the vaporization causes pressure reduction, which causes an error. However, in the present invention, a change in pressure is detected. Since this is performed after returning to the standard temperature, this kind of error is not likely to occur fundamentally. However, more surely put activated carbon in a closed container,
The generated gas should be adsorbed.

In this case, the accuracy of measurement can be improved by arranging an equal amount of activated carbon in the pressure standard container.

[0022]

[Example] As a material to be hardened, an optodyne series (product code U, which is an ultraviolet curable resin manufactured by Daikin Industries, Ltd.
V1000-4000) was used.

First, the liquid resin before curing is 0.2c with a syringe.
c was taken and placed in a petri dish 8 in a closed container 1 made of glass and having a volume of 20 cc. Then, using the glass lapped pipe 4, the closed container 1 and the standard container 2 were connected to the pressure gauge 3 to form a measuring device, which was then placed in a water tank at a temperature of 20 ° C. and left to equilibrate.

Next, after taking out from the water tank and irradiating with ultraviolet rays 6 of a light amount of 10 J / cm ² for 2 hours using a high pressure mercury lamp to cause the reaction, the reaction solution was put into a water tank at 20 ° C. and left to equilibrate. The pressure difference was measured, and the cure shrinkage ratio was calculated from this.

Table 1 shows the relationship between the measured value thus obtained and the published value of the manufacturer, and both values are the same.

[0026]

[Table 1]

[0027]

According to the present invention, highly accurate measurement can be carried out using a small amount of sample, which enables highly accurate pattern formation.

[Brief description of drawings]

FIG. 1 is a configuration diagram of a curing shrinkage rate measuring device for an ultraviolet curable resin.

FIG. 2 is a configuration diagram of a curing shrinkage measuring device for thermosetting resin.

[Explanation of symbols]

 1 Airtight container 2 Standard container 3 Pressure gauge 4 Piping 5 Energy supply source

Claims (4)

[Claims] 1. An ultraviolet ray (6) for accommodating a measurement sample
And a standard container (2) having the same material and size as the closed container (1)
And a pipe (4) between the closed container (1) and the standard container (2).
It is characterized by comprising at least a pressure gauge (3) arranged via a pressure gauge, and an energy supply source (5) for applying curing energy to the measurement sample housed in the closed container (1). Curing shrinkage measuring device. 2. The cure shrinkage ratio measuring device according to claim 1, wherein the energy supply source (5) is a heater equipped with an ultraviolet irradiation device or a temperature controller. 3. A weighed sample of a liquid resin is placed in a closed container (1), and the closed container (1) and a standard container (2).
And are connected to a pressure gauge (3) using a pipe (4) and kept at a standard temperature, and curing energy is applied to the closed container (1) and the standard container (2) from an energy supply source (5). The liquid resin in the closed container (1) is cured, the closed container (1) and the standard container (2) are returned to the standard temperature, and the pressure difference between the two is measured by the pressure gauge (3). ) Is used to determine the volume reduction of the resin due to curing, and the ratio to the previously weighed amount of the liquid resin is determined. ΔV = VΔP / (P-ΔP) (1) where ΔV is the volume reduction of the resin, V is the volume of the closed container, P is the atmospheric pressure of the closed container before the resin is cured, and ΔP is the pressure drop. amount 4. An equal amount of activated carbon is placed inside the closed container (1) or a pipe (4) connecting the container (1) to remove gas generated during the curing reaction of the resin. The method for measuring the shrinkage ratio according to claim 3.