JP6632007B1 - Method for evaluating time-dependent expansion or contraction due to curing of curable composition, coating member, method for designing curing conditions of curable composition, and method for designing curable composition - Google Patents

Abstract

An object of the present invention is to provide a method for accurately evaluating expansion or shrinkage of a curable composition due to curing. Kind Code: A1 A method for evaluating the time-dependent expansion or shrinkage due to curing of a curable composition, comprising curing a curable composition housed in a housing member and having a covering member 20 disposed on a surface thereof, From the measurement step of continuously irradiating the coating member from the laser light source X with the laser beam 13 and continuously measuring the position of the coating member based on the reflected light, and the transition of the position measured in the measurement step, the curable composition An evaluation step of evaluating time-dependent expansion or contraction due to curing of the object, wherein the coating member has a reflectance to laser light of 50% or more and a mass of 10 mg or less. [Selection diagram] Fig. 1

Description

  The present invention is a method for evaluating the time-dependent expansion or shrinkage due to curing of a curable composition, a coating member used for the above-described method, and a method for designing curing conditions for the curable composition using the above-described method, A method for designing a curable composition using the methods described above.

  2. Description of the Related Art In the manufacture of electronic devices and the like, an ultraviolet-curable composition is used as an adhesive for fixing members such as electronic components and optical components, and as a coating for protecting members. The ultraviolet curable composition can be cured in a short time by a simple operation. However, since the ultraviolet curable composition shrinks during curing, there is a problem that a deviation from the design occurs. In particular, in fixing a precision component or an optical component, even a small shrinkage ratio may cause a shift of an optical axis or the like, which may cause a trouble in an electronic device.

  As a technique for solving such a problem, the present inventor is a method for measuring the curing shrinkage of an adhesive made of an ultraviolet-curable resin, and a step of disposing the ultraviolet-curable resin on a glass plate that transmits ultraviolet light, A step of providing a laser sensor for measuring the distance in a non-contact manner on the upper part of the ultraviolet curable resin, a step of irradiating ultraviolet light from a lower part of the glass plate to cure the resin, and the laser sensor, before and after irradiation of ultraviolet light, glass Measuring the distance of the UV-curable resin from the plate surface, and the surface area of the UV-curable resin, respectively, to quantify the shrinkage state of the UV-curable resin. (See Patent Document 1). According to this resin curing shrinkage measuring method, the shrinkage ratio of the ultraviolet curable resin before and after curing can be grasped. Therefore, for example, a desired product can be manufactured by designing it in consideration of the product design.

Patent No. 5848109

  However, there is a need for improvement in distance measurement accuracy in order to evaluate curing shrinkage of an ultraviolet curable composition with higher accuracy. In particular, a transparent ultraviolet curable composition having a low reflectance with respect to laser light has a problem that it is difficult to measure an accurate distance and to accurately grasp a contracted state of the ultraviolet curable composition. Further, in order to manufacture more precise electronic equipment, it is desired that shrinkage of the ultraviolet curable composition can be more accurately evaluated. And an ultraviolet curable composition may expand by hardening.

  Note that a photocurable composition that is cured by light other than ultraviolet light, a curable composition that is cured by energy other than light, such as a thermosetting composition that is cured by heat, and a curable composition that is cured by moisture. And the like can be used as the above-mentioned adhesives and coatings similarly to the ultraviolet curable composition, and there is a problem such as shrinkage at the time of curing similarly to the ultraviolet curable composition.

The present invention has been made in view of the above circumstances, and has as its object to provide a method and means capable of accurately evaluating expansion or shrinkage due to curing of a curable composition.
Another object of the present invention is to provide a method for designing curing conditions for curing a curable composition as desired, and a method for designing a curable composition to cure as desired.

  The present inventors cured the curable composition in a state where the coating member having a correspondingly high reflectance to laser light and a correspondingly low mass was placed on the surface of the curable composition, and continuously cured the coating member. By irradiating the laser light, the position of the covering member is continuously measured based on the reflected light, and by evaluating the time-dependent expansion or contraction due to curing of the curable composition from the transition of the measured position, The inventors have found that the problem can be solved, and have completed the present invention. More specifically, the present invention provides the following.

(1) A method for evaluating the time-dependent expansion or shrinkage due to curing of a curable composition,
While curing the curable composition contained in the containing member and having the covering member disposed on the surface, continuously irradiating the covering member with a laser beam from a laser light source, the position of the covering member based on the reflected light. A measuring step of continuously measuring
From the transition of the position measured in the measurement step, including an evaluation step of evaluating the expansion or contraction over time due to the curing of the curable composition,
The method, wherein the coating member has a reflectance of 50% or more to the laser light and a mass of 10 mg or less.

  (2) The method according to (1), wherein the covering member is disposed so as not to contact the housing member.

  (3) The measuring step includes an infrared ray amount measuring step of continuously measuring the amount of infrared rays emitted from the coating member in a non-contact manner, and the evaluating step includes measuring the infrared ray amount measured in the infrared ray amount measuring step. The method according to (1) or (2), further comprising a temperature evaluation step of evaluating a temperature change over time due to curing of the curable composition from a change in the amount of infrared rays.

  (4) A covering member used in the method according to any one of (1) to (3), comprising a rigid film having a mass of 10 mg or less.

(5) The covering member according to (4), wherein the thermal conductivity is 70 Wm ^-1 K ^-1 or more.

  (6) The covering member according to (5), comprising an inorganic material.

  (7) The covering member according to any one of (4) to (6), having a black body on at least a part of the main surface.

  (8) The covering member according to any one of (4) to (7), which has a thickness of 100 µm or less.

  (9) Curing of the curable composition based on evaluation information of expansion or contraction over time due to curing of the curable composition obtained by the method according to any one of (1) to (3). How to design conditions.

  (10) The curable composition is designed based on the evaluation information of the time-dependent expansion or shrinkage due to curing of the curable composition obtained by the method according to any one of (1) to (3). how to.

According to the method for evaluating expansion or contraction of a curable composition over time due to curing of the curable composition of the present invention, it is possible to accurately evaluate expansion or contraction of the curable composition due to curing.
Then, based on the evaluation information obtained by this method, the curing conditions of the curable composition can be designed, and the curable composition can be designed.

It is a typical sectional view showing an example of the measuring device which can be used by the method of evaluating expansion or contraction with time by hardening of the photocurable composition. It is a schematic diagram explaining a covering member. It is a typical sectional view showing other examples of a measuring device which can be used by the method of evaluating expansion or contraction with time by hardening of a photocurable composition. It is a figure showing an example of a measuring device which can be used in a method of evaluating expansion or contraction of a thermosetting composition over time due to curing. FIG. 7 is a diagram showing the results of Example 1. FIG. 9 is a diagram showing the results of Comparative Example 1.

  Hereinafter, embodiments of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments.

<<< Method for evaluating temporal expansion or shrinkage due to curing of curable composition >>>
The method for evaluating the time-dependent expansion or shrinkage due to curing of the curable composition of the present invention is a method for curing a curable composition which is housed in a housing member and has a coating member disposed on the surface, and a coating member from a laser light source. Irradiating the laser beam continuously, and the measuring step of continuously measuring the position of the covering member based on the reflected light, from the transition of the position measured in the measuring step, the temporal change due to curing of the curable composition An evaluation step of evaluating expansion or contraction, wherein the coating member has a reflectance to laser light of 50% or more and a mass of 10 mg or less.

  The curable composition to be evaluated is not particularly limited as long as it contains a component to be cured. Typically, a photocurable composition containing a component curable by light such as ultraviolet light, a thermosetting composition containing a component curable by heat, a mixture of a photocurable composition and a thermosetting composition, air A moisture-curable composition containing a component that reacts with moisture in the composition to cure, and a curable composition composed of a mixture of two or more liquids (eg, a curable composition used as a two-part adhesive). Can be Hereinafter, the case where the photocurable composition is evaluated and the case where the thermosetting composition is evaluated will be described as examples.

<Method for evaluating temporal expansion or shrinkage due to curing of photocurable composition>
A method for evaluating the time-dependent expansion or contraction due to curing of the photocurable composition will be described with reference to FIGS. FIG. 1 is a schematic cross-sectional view showing an example of a measuring device that can be used in a method of evaluating expansion or contraction of a photocurable composition over time due to curing. 2A and 2B are schematic views illustrating a covering member, FIG. 2A is a cross-sectional view, FIG. 2B is a top view, and FIG. 2C is a cross-sectional view illustrating another example. is there.

  As shown in FIG. 1, a measuring device 10 includes a measuring table 12 on which a photocurable composition 11 as a curable composition is mounted, and a laser light source provided on the photocurable composition 11 mounted on the measuring table 12. A displacement meter 14 that continuously measures a distance a (position) to a covering member 20 by irradiating a laser beam 13 from X and detecting a reflected light thereof, and a photocurable composition placed on a measurement table 12. A light irradiation device 16 for irradiating the object 11 with the light 15 to the photocurable composition 11 from the measurement table 12 side to cure the photocurable composition 11;

  In FIG. 1, the measurement table 12 is made of a material (for example, glass) that transmits light 15. In FIG. 1, an embodiment in which an ultraviolet curable composition containing a component curable by ultraviolet light is used as the photocurable composition 11, an ultraviolet irradiation device is used as the light irradiation device 16, and ultraviolet light is irradiated as the light 15. Is shown. Note that ultraviolet light refers to light having a wavelength of 10 nm to 400 nm.

  In the method for evaluating the time-dependent expansion or shrinkage due to curing of the photocurable composition, the photocurable composition 11 as the curable composition is first placed in the housing member 17 using such a measuring device 10. (Accommodation step). The housing step is an optional component of the method of the present invention.

The photo-curable composition 11 only needs to contain a photo-curable component that is cured by light irradiation. Examples of the photocurable component include (meth) acrylates and epoxy compounds, and one type or two or more types may be used. The (meth) acrylate becomes an acrylic resin by light curing, and the epoxy compound becomes an epoxy resin by light curing. In this specification, the term “(meth) acryl” is used to mean “acryl and / or methacryl”.
In addition, the photocurable composition 11 may include an additive usually contained in the photocurable composition. Examples of the additive include a filler, a catalyst, a polymerization initiator, a curing agent, and the like.

  The shape of the housing member 17 is not particularly limited as long as the photocurable composition 11 can be housed therein and the photocurable composition 11 can be irradiated with the laser light 13 and the light 15. As shown in FIG. 2A and FIG. 2B, a ring-shaped housing member can be used. Alternatively, as shown in FIG. 2C, a housing member having a bottom portion 19 without the housing portion of the photocurable composition 11 penetrating therethrough may be used.

  The material of the housing member 17 is not particularly limited, but is preferably a material to which the photocurable composition 11 is difficult to adhere. When the photocurable composition 11 adheres to the housing member 17, when the photocurable composition 11 expands or contracts due to curing, a stress corresponding to the expansion or contraction is generated, so that the photocurable composition 11 expands or contracts. Is to be affected. Examples of the material to which the photocurable composition 11 is difficult to adhere include a fluororesin such as Teflon (registered trademark).

  The photocurable composition 11 is preferably housed in the housing member 17 such that the surface on the side irradiated with the laser light 13 is smooth. When the surface of the photocurable composition 11 is smooth, the distance a can be measured more accurately by placing the flat covering member 20 thereon. However, when the photocurable composition 11 maintains shape retention throughout the curing process, expansion or contraction occurs while maintaining the surface shape, so that the problem is small even if the surface is not smooth.

  The housing member 17 housing the photocurable composition 11 is installed at a predetermined position on the measuring table 12, and is positioned by a positioning member 18 as needed.

  In the case of using a hollow (for example, a ring) -shaped accommodation member 17, for example, after the accommodation member 17 is set and mounted on the measurement table 12, the accommodation member 17 is filled with the photocurable composition 11, or light 15 is applied. The photocurable composition 11 may be stored in the housing member 17 by placing the housing member 17 on the transparent plate member and then filling the housing member 17 with the photocurable composition 11.

  Next, the covering member 20 is arranged on the surface of the photocurable composition 11 housed in the housing member 17 (covering member arrangement step). The covering member arranging step is an optional component in the method of the present invention.

The covering member 20 disposed on the surface of the photocurable composition 11 accommodated in the accommodating member 17 has a reflectance of 50% or more and a mass of 10 mg or less with respect to the laser light 13 irradiated in the subsequent measurement step.
When the reflectance with respect to the laser light 13 is insufficient, the laser light 13 absorbs a large amount, and the distance a may not be accurately measured in a subsequent measurement step. The lower limit of the reflectance to laser light may be 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, or 90% or more. Moreover, the upper limit of the reflectance with respect to the laser beam is not particularly limited, and may be 100% or less, or 95% or less.
If the mass of the covering member 20 is excessive, the surface of the photocurable composition 11 on which the covering member 20 is placed is pressed due to its own weight, and depending on the viscosity of the photocurable composition 11 during the curing process, The photocurable composition 11 swells from between the housing 20 and the housing member 17, making it difficult to measure the distance accurately. The mass of the covering member is preferably 8.0 mg or less, more preferably 6.0 mg or less, and still more preferably 3.0 mg or less. The lower limit of the mass of the covering member 20 is not particularly limited, and may be, for example, 0.1 mg or more, 0.5 mg or more, or 1.0 mg or more.

  It is preferable that the covering member 20 is a rigid body having shape retaining properties that does not lose its shape in the measurement step. If the covering member 20 itself deforms during the measurement process, the distance a may change due to the deformation of the covering member 20 itself. However, by using a rigid body that does not deform itself, the accurate distance a can be obtained. Note that the deformation here does not mean a deformation (bending or the like) due to an external force.

  It is preferable that the thickness of the covering member 20 is 100 μm or less. When the photocurable composition 11 is cured, a temperature change occurs, and the temperature change may change the thickness of the coating member 20. In order to reduce the influence of the change in thickness, the coating member 20 has a thickness of 100 μm. It is preferable to be as thin as the following. The thickness of the covering member 20 is preferably 75 μm or less, more preferably 50 μm or less, further preferably 25 μm or less, and particularly preferably 15 μm or less. In addition, the thickness here is an average value of the thickness of the covering member.

  Further, it is preferable that the surface of the covering member 20 that is in contact with the curable composition is a material that is chemically stable to the curable composition. Therefore, it is preferable that the covering member 20 is typically made of an inorganic material such as a metal. Examples of the metal include aluminum, iron, silicon, copper, silver, and gold.

  The covering member 20 is preferably a metal foil.

  The covering member 20 may be composed of a single member, or may be composed of a plurality of members (consisting of a base material and other members (for example, a black body described later)). In the latter case, the above description of the covering member 20 applies to both the base member and the plurality of members.

  It is preferable that such a covering member 20 is arranged so as not to contact the housing member 17. This is because when the covering member 20 comes into contact with the housing member 17, friction occurs between the covering member 20 and the housing member 17, which affects the expansion or contraction of the photocurable composition 11. In other words, the covering member 20 is the same size as or smaller than the opening of the housing member 17. The latter is preferable from the viewpoint of simply preventing the contact, while the coating member 20 is disadvantageous in that, as the covering member 20 becomes smaller, the area of the photocurable composition 11 where the temporal expansion or contraction can be evaluated becomes narrower. obtain. For this reason, the lower limit of the sectional area of the covering member 20 with respect to the opening area of the housing member 17 is 25% or more, 35% or more, 45% or more, 55% or more, 65% or more, 75% or more, 85% or more, or 90% or more. % Or less, and the upper limit is preferably 99% or less, 98% or less, 97% or less, 96% or less, or 95% or less. From this viewpoint, the material of the covering member 20 is typically a metal (platinum, iron, brass, aluminum, gold, silver, copper), but may be a colored resin composition or the like.

  Next, the photocurable composition 11 on which the covering member 20 is disposed is irradiated with light 15 as energy to cure the photocurable composition 11, and a laser beam is continuously applied to the covering member 20 from the laser light source X. The light 13 is irradiated, and the position (distance a) of the covering member 20 is continuously measured based on the reflected light (measuring step).

  When the photocurable composition 11 is irradiated with light 15, the photocurable composition 11 expands first, and then contracts as curing proceeds. In addition, the photocurable composition 11 that reacts and cures quickly may start to contract immediately upon irradiation with the light 15.

  As described above, since the photocurable composition 11 expands and contracts when it is cured by irradiation with the light 15, the volume changes between the irradiation of the light 15 and the completion of the curing. In FIG. 1, the photocurable composition 11 is housed in a housing member 17 and has a substantially constant cross-sectional area. Changes. Then, similarly to the change in the thickness of the photocurable composition 11, the position of the covering member 20 placed on the surface of the photocurable composition 11 changes. Similarly to the change, the distance a to the covering member 20 also changes. That is, when the thickness of the photocurable composition 11 decreases, the distance a increases by an amount corresponding to the decrease. In addition, depending on the required accuracy, it is necessary to consider a change in the cross-sectional area of the photocurable composition 11 due to expansion and contraction of the housing member 17, and in that case, the cross-sectional area of the photocurable composition 11 is also measured. The change in volume of the photocurable composition 11, that is, expansion or contraction, can also be evaluated in consideration of the cross-sectional area in addition to the thickness.

  Therefore, in the measurement process, when the photocurable composition 11 is cured by irradiating the light 15, the laser light source X continuously irradiates the coating member 20 with the laser light 13, and based on the reflected light, the coating member 20 is irradiated. Is obtained by continuously measuring the position (distance a) of the photocurable composition 11 from the irradiation of the light 15 to the completion of the curing (that is, transition information). Can be. Note that the distance a may be measured over the entire period from the irradiation of the light 15 to the completion of the curing, but the measurement period is arbitrarily selected according to the period for which the thickness change information is to be known. do it.

Here, when the distance from the displacement meter 14 to the surface of the photocurable composition 11 is to be measured without using the covering member 20, the laser light 13 of the photocurable composition such as a transparent photocurable composition is used. When the reflectance with respect to is low, it is difficult to measure an accurate distance, and there is a problem that the shrinkage or expansion state of the photocurable composition may not be accurately grasped.
However, in the present invention, the covering member 20 is disposed on the surface of the photocurable composition 11, and since the covering member 20 has a reflectance of 50% or more with respect to the laser beam 13, the position (distance) of the covering member 20 a) can be measured accurately. In addition, by placing the covering member 20, the light 15 is reflected by the covering member 20, the curing of the photocurable composition 11 proceeds efficiently, and the measurement sensitivity is increased.

  The laser beam 13 to be irradiated is not particularly limited, but is, for example, light having a wavelength of 500 nm or more and 700 nm or less.

  The continuous irradiation of the laser beam 13 from the laser light source X to the covering member 20 may be intermittent or continuous.

  Next, from the transition of the distance a measured in the measurement step, the time-dependent expansion or contraction due to the curing of the photocurable composition 11 is evaluated (evaluation step).

For example, in the measurement process, the relative positions of the displacement meter 14 including the laser light source X and the measurement table 12 are fixed, the thickness b of the covering member 20, the distance c between the displacement meter 14 and the surface of the measurement table 12, and the measurement process. The thickness T of the photocurable composition 11 is determined using the transition information of the distance a measured in the above, and the curing shrinkage is determined by the following equation (1).
_{A (t) = (T 0} -T (t)) / T 0 × 100 (%) ··· (1)
A (t): Curing shrinkage rate (%) at time t under arbitrary curing conditions
t: elapsed time T ₀ after the start of curing: initial film thickness at t = 0 (at the start of curing) T (t): film thickness at time t under arbitrary curing conditions

  By determining the curing shrinkage ratio A at an arbitrary time t in this manner, the expansion or shrinkage of the photocurable composition 11 over time due to curing can be evaluated (understood). For example, when the difference between the curing shrinkage at time t (second) and the curing shrinkage at time t + 300 (second) becomes extremely small, it may be determined that t + 300 (second) is the time required for completing the curing. it can.

In the above equation (1), the curing start time is used as a reference. However, instead of the curing start time, the irradiation start time may be used as a reference, and for example, the curing shrinkage may be obtained by the following equation (2).
A (t ′) = (T ₀ ′ −T (t ′)) / T ₀ ′ × 100 (%) (2)
A (t '): Curing shrinkage rate (%) at time t' under arbitrary curing conditions
t ′: elapsed time after irradiation T ₀ ′: initial film thickness at t ′ = 0 (at the start of irradiation) T (t ′): film thickness at time t ′ under arbitrary curing conditions

  Further, in the above description, an example in which the curing shrinkage rate is obtained based on the thickness T to evaluate the expansion or shrinkage of the photocurable composition 11 over time due to curing is shown. Since there is a correlation with the thickness T of No. 11, expansion or shrinkage over time due to curing of the photocurable composition may be evaluated at the distance a.

  Further, in the method for evaluating the time-dependent expansion or contraction due to curing of the photocurable composition, the measuring step includes an infrared amount measuring step of continuously measuring the amount of infrared radiation emitted from the coating member in a non-contact manner. The evaluation step may include a temperature evaluation step of evaluating a change in temperature over time due to curing of the curable composition from a change in the amount of infrared light measured in the step of measuring the amount of infrared light. An embodiment in which the measurement step includes the infrared ray amount measurement step and the evaluation step includes the temperature evaluation step will be described with reference to FIG. FIG. 3 is a schematic cross-sectional view showing another example of a measuring device that can be used in a method of evaluating expansion or contraction of a photocurable composition over time due to curing. In FIG. 3, the same members as those in FIG. 1 are denoted by the same reference numerals, and redundant description is omitted. As shown in FIG. 3, the measuring device 30 is a measuring device provided with an infrared ray measuring device 31 in the measuring device 10 of FIG.

  More specifically, the measuring device 30 includes an infrared light amount measuring device 31 that measures the amount of infrared light 32 emitted from the covering member 20. It is possible to measure the temperature of the coating member 20 in a non-contact manner by measuring the amount of the infrared light 32 radiated from the coating member 20 with the infrared ray measuring device 31 and considering the thermal emissivity (known) of the coating member 20. it can.

  Then, in the measuring step, the amount of infrared rays 32 emitted from the covering member 20 is continuously measured in a non-contact manner using the measuring device 30 of FIG. 3 (infrared ray measuring step), and in the evaluating step, the amount of infrared ray is measured. From the change in the amount of infrared rays measured in the step, the temperature change over time due to the curing of the photocurable composition is evaluated (temperature evaluation step).

  Here, when the photocurable composition 11 is irradiated with the light 15, the photocurable composition 11 is cured. As the photocurable composition 11 cures, the temperature of the photocurable composition 11 changes. Then, the covering member 20 is disposed on the surface of the photocurable composition 11. That is, the photocurable composition 11 and the covering member 20 are in contact with each other. Therefore, since the heat of the photocurable composition 11 is conducted to the coating member 20, the temperature of the coating member 20 changes with the temperature change of the photocurable composition 11.

  Therefore, in the measurement step, when the photocurable composition 11 is cured by irradiating the light 15, the amount of the infrared light 32 radiated from the covering member 20 is continuously measured in a non-contact manner, so that the light 15 is Temperature change information (that is, transition information) of the temperature of the photocurable composition 11 from irradiation to completion of curing can be obtained. In addition, the amount of the infrared rays 32 may be measured over the entire period from the irradiation of the light 15 to the completion of the curing, but the measurement period is arbitrarily set in accordance with the period in which the temperature change information is to be known. Just select.

  The temperature of the photocurable composition 11 may change abruptly due to chemical energy or the like generated in the reaction process, and may not be sufficiently controlled only by monitoring the external temperature. The temperature of the photocurable composition 11 affects the volatility of the curable component (which may adversely affect the actual production environment) and the activity of the catalyst component (not only the magnitude of the activity but also deterioration such as deactivation). ), It is important to grasp the transition.

The covering member 20 preferably has a thermal conductivity of 70 Wm ⁻¹ K ⁻¹ or more. When the thermal conductivity is 70 Wm ⁻¹ K ⁻¹ or more, since the heat of the photocurable composition 11 is easily transmitted to the coating member 20, it is possible to more accurately evaluate the temperature change information of the photocurable composition 11. it can. The lower limit of the thermal conductivity is not particularly ^{limited, 72Wm -1 K} -1 or higher (e.g. ^{platinum), 80Wm -1 K} -1 or higher (e.g. ^{iron), 90Wm -1 K} -1 or higher (for example, nickel), 100Wm ^-1 K ^-1 or higher (e.g. brass), ^{150 Wm} -1 ^{K -1} or higher (e.g., silicon), ^{200 Wm} -1 ^{K -1} or higher, or ^230Wm -1 ^{K -1} or higher (e.g. aluminum, gold, copper, silver) that is Is preferred.

  Preferably, the covering member 20 has a black body on at least a part of the main surface. The main surface is a surface on which the amount of the infrared light 32 is measured. Since the thermal emissivity of the black body is high and the amount of change in infrared rays with respect to the temperature change of the covering member 20 is large, the temperature of the covering member 20 can be measured more accurately.

  Examples of the black body include graphite. The method for providing the black body on the covering member 20 is not particularly limited, and for example, a black body may be applied.

Based on the evaluation information of the expansion or shrinkage of the photocurable composition over time obtained by curing the photocurable composition, curing conditions for the photocurable composition, for example, conditions for supplying light to the photocurable composition Can be designed.
Specifically, it is possible to determine whether or not the light supply history (supply amount, timing, total time) is appropriate based on the evaluation information of the time-dependent expansion or contraction due to curing of the photocurable composition. And a desired curing can be achieved. For example, if the final expansion or contraction was unacceptable, it may be appropriate to reduce the amount of light delivered or the total time. Further, when the speed of expansion or contraction in the middle is too high, it may be appropriate to reduce the light supply amount at that timing (that is, make the light supply speed gentle).

  In addition, when the temperature change of the photocurable composition is evaluated, it is possible to determine whether or not the light supply history (supply amount, timing, total time) is appropriate based on the information, and to determine the desired curing. And a hardening environment can be realized. For example, when the temperature in the middle is too high, it may be appropriate to reduce the light supply amount at that timing (that is, make the light supply speed moderate).

Further, the photocurable composition can be designed based on the thus obtained evaluation information of the time-dependent expansion or shrinkage due to the curing of the photocurable composition.
Specifically, the composition of the photocurable composition (for example, the type and amount of polymerization initiator, the type and amount of polymerization inhibitor, , Filler type, particle size, amount, etc.) can be determined, and desired curing can be realized. For example, if the expansion or shrinkage is below the allowable limit, change the polymerization initiator species to more reactive species, increase the amount, or change the polymerization inhibitor species to lower inhibition performance species Or reduce the amount, or reduce the amount of filler. If the swelling or shrinking is unacceptable, change the polymerization initiator species to a less reactive species, reduce the amount, or change the polymerization inhibitor species to a more forbidden species. Or the amount of filler or the amount of filler can be increased.

  In addition, when evaluating the temperature change of the photocurable composition, based on the information, the composition of the photocurable composition (for example, the type and amount of the polymerization initiator, the type and amount of the polymerization inhibitor, the type of the filler, (E.g., particle size and amount) can be determined, and a desired curing or curing environment can be realized. For example, if the temperature in the middle is too high, a monomer having a high volatilization temperature can be employed, or a catalyst having high temperature durability can be used.

<Method of evaluating temporal expansion or contraction due to curing of thermosetting composition>
A method of evaluating expansion or shrinkage over time due to curing of the thermosetting composition will be described with reference to FIG. FIG. 4 is a schematic cross-sectional view showing an example of a measuring device that can be used in a method of evaluating expansion or contraction over time due to curing of a thermosetting composition. 4, the same members as those in FIG. 1 are denoted by the same reference numerals, and overlapping description is omitted. As shown in FIG. 4, the measuring device 40 is a device for measuring the thermosetting composition 41. In the measuring device 10 of FIG. 1, a heating / cooling device 42 is provided instead of the light irradiation device 16, and the measurement is performed. This is a measuring device using a measuring table 43 instead of the table 12.

  More specifically, the measuring device 40 has a heating / cooling device 42 for curing the thermosetting composition 41 by heating or cooling the thermosetting composition 41 stored in the storage member 17. The measuring table 43 of the measuring device 40 is made of a material whose temperature can be adjusted by the heating / cooling device 42.

  In the method for evaluating the expansion or shrinkage of the thermosetting composition over time due to curing, the thermosetting composition 41 as the curable composition is first placed in the housing member 17 using such a measuring device 40. (Accommodation step). The housing step is an optional component of the method of the present invention.

The thermosetting composition 41 may include a thermosetting component that is cured by heat. Examples of the thermosetting component include (meth) acrylates and epoxy compounds, and one type or two or more types may be used. The (meth) acrylate generates an acrylic resin by thermosetting, and the epoxy compound generates an epoxy resin by thermosetting.
In addition, the thermosetting composition 41 may include an additive usually contained in the thermosetting composition. Examples of the additive include a filler, a catalyst, a polymerization initiator, a curing agent, and the like.

  The housing member 17 is the same as that used in the method for evaluating the time-dependent expansion or shrinkage due to curing of the photocurable composition, except that it is preferably a material that is not easily deformed by heat.

  The housing member 17 housing the thermosetting composition 41 is installed at a predetermined position on the measuring table 12, and is positioned by the positioning member 18 as necessary.

  When a hollow (for example, ring-shaped) housing member 17 is used, for example, after the housing member 17 is set and mounted on the measurement table 12, the housing member 17 is filled with the thermosetting composition 41, or a plate-shaped member. The thermosetting composition 41 may be stored in the housing member 17 by filling the housing member 17 with the thermosetting composition 41 after placing the housing member 17 thereon.

  Next, the covering member 20 is arranged on the surface of the thermosetting composition 41 housed in the housing member 17 (covering member arranging step). The covering member arranging step is an optional component in the method of the present invention.

  The covering member 20 disposed on the surface of the thermosetting composition 41 accommodated in the accommodating member 17 is the same as that used in the method for evaluating the temporal expansion or shrinkage due to the curing of the photocurable composition.

  It is preferable that such a covering member 20 is arranged so as not to contact the housing member 17. This is because, when the covering member 20 comes into contact with the housing member 17, friction occurs between the covering member 20 and the housing member 17, which affects the expansion or contraction of the thermosetting composition.

  Next, heat as energy is supplied to the thermosetting composition 41 in which the covering member 20 is disposed, that is, the thermosetting composition 41 is heated to cure the thermosetting composition 41 and from the laser light source X to the covering member 20. The laser beam 13 is continuously irradiated, and the distance a (the position of the covering member 20) from the displacement meter 14 to the covering member 20 is continuously measured based on the reflected light (measuring step).

  When the thermosetting composition 41 is heated, the thermosetting composition 41 expands during the temperature rise, starts to contract when the curing temperature is reached and curing starts, and continues to contract until returning to room temperature.

  As described above, since the thermosetting composition 41 expands and contracts when it is cured by heating, the volume changes between the time of heating and the time of completion of curing. In FIG. 4, since the thermosetting composition 41 is contained in the containing member 17, the thickness of the thermosetting composition 41 changes from heating to completion of curing. Then, similarly to the change in the thickness of the thermosetting composition 41, the position of the covering member 20 placed on the surface of the thermosetting composition 41 changes, so that the thickness of the thermosetting composition 41 decreases. Similarly to the change, the distance a to the covering member 20 also changes. That is, when the thickness of the thermosetting composition 41 is reduced, the distance a is increased by the reduced thickness.

  Therefore, in the measurement step, when the thermosetting composition 41 is cured by heating, the laser light source X continuously irradiates the coating member 20 with the laser light 13 and the position of the coating member 20 (based on the reflected light). By continuously measuring the distance a), it is possible to obtain change information (that is, transition information) of the thickness of the thermosetting composition 41 during the period from heating to completion of curing. Note that the distance a may be measured over the entire period from heating to completion of curing, but the measurement period may be arbitrarily selected according to the period for which thickness change information is to be known. .

Here, when the distance from the displacement meter 14 to the surface of the thermosetting composition 41 is to be measured without using the covering member 20, the laser light 13 of the thermosetting composition such as a transparent thermosetting composition is used. If the reflectance with respect to the thermosetting composition 41 is low, it is difficult to measure an accurate distance, and there is a problem that the contraction or expansion state of the thermosetting composition 41 may not be accurately grasped.
However, in the present invention, the covering member 20 is disposed on the surface of the thermosetting composition 41, and since the covering member 20 has a reflectance of 50% or more with respect to the laser beam 13, the position (distance) of the covering member 20 a) can be measured accurately. In addition, since the placement of the covering member 20 makes it difficult for heat to escape, the curing of the thermosetting composition 41 proceeds efficiently, and there is also an effect that the measurement sensitivity is increased.

  The laser beam 13 to be applied is the same as that used in the method for evaluating the time-dependent expansion or contraction due to the curing of the photocurable composition.

  The continuous irradiation of the laser beam 13 from the laser light source X to the covering member 20 may be intermittent or continuous.

  Next, from the transition of the distance a measured in the measurement step, the expansion or contraction of the thermosetting composition 41 over time due to curing is evaluated (evaluation step). The evaluation step is the same as the evaluation step in the method for evaluating the time-dependent expansion or contraction due to curing of the photocurable composition.

  In addition, the measuring step includes an infrared amount measuring step of continuously measuring the amount of infrared radiation emitted from the covering member in a non-contact manner, and the evaluation step is based on a change in the amount of infrared light measured in the infrared amount measuring step. The method may include a temperature evaluation step of evaluating a temperature change over time due to curing of the curable composition. When the measuring step includes the infrared ray measuring step and the evaluating step includes the temperature evaluating step, a measuring apparatus provided with the infrared measuring apparatus 31 in FIG. 3 for the measuring apparatus 40 in FIG. 4 may be used. .

  Then, the amount of the infrared rays 32 radiated from the covering member 20 is continuously measured in a non-contact manner in the measuring step by using a measuring device provided with the infrared ray measuring device 31 in FIG. 3 as the measuring device 40 in FIG. Then, in the evaluation step, the change in the temperature over time due to the curing of the thermosetting composition is evaluated from the change in the amount of infrared light measured in the step of measuring the amount of infrared light in the evaluation step (temperature evaluation step).

  Here, when the thermosetting composition 41 is heated, the temperature of the thermosetting composition 41 changes according to the heating and curing reaction. The covering member 20 is disposed on the surface of the thermosetting composition 41. That is, the thermosetting composition 41 and the covering member 20 are in contact with each other. Therefore, since the heat of the thermosetting composition 41 is conducted to the coating member 20, the temperature of the coating member 20 changes with the temperature change of the thermosetting composition 41.

  Therefore, in the measurement step, when the thermosetting composition 41 is cured by heating, the amount of the infrared rays 32 radiated from the covering member 20 is continuously measured in a non-contact manner, so that the heat radiation of the covering member 20 is measured. From the rate, it is possible to obtain temperature change information (that is, transition information) of the temperature of the thermosetting composition 41 during the period from heating to completion of curing. When evaluating a thermosetting composition, the temperature has a great influence on the curing reaction, and thus the importance of evaluating the temperature change is even higher. The amount of infrared rays 32 may be measured over the entire period from heating to completion of curing, but the measuring period may be arbitrarily selected in accordance with the period for which information on temperature change is desired. Good.

  The covering member 20 is the same as that used in the method for evaluating the time-dependent expansion or contraction due to curing of the photocurable composition.

  When the curable composition to be evaluated is a mixture of the photocurable composition and the thermosetting composition, the measurement is performed by further providing the heating / cooling device 42 of FIG. 4 to the measuring device 10 of FIG. By using a device or a measuring device provided with the heating / cooling device 42 of FIG. 4 in the measuring device 30 of FIG. 3, expansion or contraction of the curable composition over time due to curing can be evaluated.

  The method of designing heat supply conditions to the thermosetting composition and the method of designing the thermosetting composition based on the information obtained by the above evaluation methods are the same as those of the photocurable composition (replace light with heat). ), And the description is omitted.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Example 1)
Under the following conditions, expansion or shrinkage of the photocurable composition 11 over time due to curing was evaluated using the measuring apparatus 10 of FIG. The measurement conditions are as follows.
<Condition>
Photocurable composition 11: acrylic resin (trade name: U-1542J, manufactured by Chemitech)
Housing member 17: Ring member made of Teflon (registered trademark) having an inner diameter of 10.0 mm, an outer diameter of 30 mm, and a thickness of 1.0 mm Covering member 20: An aluminum foil having a mass of 2.5 mg and a thickness of 11 μm ： Glass plate member Light irradiation device (ultraviolet irradiation device) 16 ： UV-LED
UV irradiation conditions: wavelength 365 nm, illuminance 200 mW / cm ² , irradiation time 30 seconds (s)
Measurement interval of distance a: 1 second Measurement time of distance a: 120 seconds from the start of irradiation Curing shrinkage (shrinkage): The following formula was used for calculation.
_{A (t) = (V 0} -V (t)) / V 0 × 100 (%)
= (T ₀ −T (t)) / T ₀ × 100 (%)
A (t): Curing shrinkage rate (%) at time t under arbitrary curing conditions
t: elapsed time after the start of curing V ₀ : initial volume at t = 0,
V ₀ = T ₀ × S
V (t): volume at time t,
V (t) = T (t) × S
S: Sample cross-sectional area T ₀ : Initial film thickness at t = 0 T (t): Film thickness at time t under arbitrary curing conditions The results are shown in FIG.

(Comparative Example 1)
The same operation as in Example 1 was performed except that the covering member 20 was not placed on the surface of the photocurable composition 11. FIG. 6 shows the results.

As shown in FIG. 5, in Example 1 in which the covering member 20 was disposed on the surface of the photocurable composition 11 and the position (distance a) of the covering member 20 was obtained, shrinkage due to curing could be appropriately detected. Was.
On the other hand, as shown in FIG. 6, in Comparative Example 1 in which the position (distance) of the photocurable composition 11 was obtained without disposing the covering member 20 on the surface of the photocurable composition 11, the composition actually shrunk. Despite this, the shrinkage ratio became a negative value (ie, expansion), and it was not possible to properly detect shrinkage due to curing.

10, 30, 40 Measuring device 11 Photocurable composition 12, 43 Measuring table 13 Laser beam 14 Displacement meter 15 Light 16 Light irradiation device 17 Housing member 18 Positioning member 19 Bottom 20 Coating member 31 Infrared ray measuring device 32 Infrared 41 Heat Curable composition 42 Heating / cooling device X Laser light source

Claims (19)

A method of evaluating expansion or contraction over time due to curing of the curable composition,
While curing the curable composition contained in the containing member and having the covering member disposed on the surface, continuously irradiating the covering member with a laser beam from a laser light source, the position of the covering member based on the reflected light. A measuring step of continuously measuring
From the transition of the position measured in the measurement step, including an evaluation step of evaluating the expansion or contraction over time due to the curing of the curable composition,
The measuring step has an infrared amount measuring step of continuously measuring the amount of infrared radiation emitted from the coating member in a non-contact manner,
The evaluation step includes a temperature evaluation step of evaluating a time-dependent temperature change due to the curing of the curable composition from the transition of the infrared ray amount measured in the infrared ray amount measurement step,
The covering member has a substrate,
The substrate has a reflectance of 50% or more to the laser light,
The covering member, the mass is Ri der less 10 mg,
The method, wherein a cross-sectional area of the covering member with respect to an opening area of the storage member is 99% or less.   A method for evaluating the time-dependent expansion or shrinkage due to curing of a curable composition (however, excluding a photocurable composition),
  While curing the curable composition contained in the containing member and having the covering member disposed on the surface, continuously irradiating the covering member with a laser beam from a laser light source, the position of the covering member based on the reflected light. A measuring step of continuously measuring
  From the transition of the position measured in the measurement step, including an evaluation step of evaluating the expansion or contraction over time due to the curing of the curable composition,
  The covering member has a substrate,
  The substrate has a reflectance of 50% or more to the laser light,
  The method wherein the coating member has a mass of 10 mg or less.   A method of evaluating expansion or contraction over time due to curing of the curable composition,
  While curing the curable composition contained in the containing member and having the covering member disposed on the surface, continuously irradiating the covering member with a laser beam from a laser light source, the position of the covering member based on the reflected light. A measuring step of continuously measuring
  From the transition of the position measured in the measurement step, including an evaluation step of evaluating the expansion or contraction over time due to the curing of the curable composition,
  The covering member has a substrate,
  The substrate has a reflectance of 50% or more to the laser light,
  The coating member has a mass of 10 mg or less,
  The coating member has a thickness of 100 μm or less,
  The method, wherein a cross-sectional area of the covering member with respect to an opening area of the storage member is 35% or more. The method according to any one of claims 1 to 3, wherein the covering member is arranged so as not to contact the housing member. The measuring step has an infrared amount measuring step of continuously measuring the amount of infrared radiation emitted from the coating member in a non-contact manner,
The said evaluation process includes the temperature evaluation process which evaluates the temperature change with time by hardening of the said curable composition from the transition of the said infrared-ray amount measured in the said infrared-ray amount measurement process, The Claims 2 or 3 . the method of. It is a coating member consisting of only the base material, or consisting of the base material and other members,
When consisting of only the base material, the base material is a rigid film having a mass of 10 mg or less,
When it consists of the said base material and the said other member, the several members which consist of the said base material and the said other member are rigid films with a mass of 10 mg or less, The Claims any one of Claims 1-5 . Coating member used in the method. The covering member according to claim 6 , wherein the thermal conductivity of the base material is 70 Wm ^-1 K ^-1 or more. The covering member according to claim 7 , wherein the base material is made of an inorganic material. The covering member according to any one of claims 6 to 8 , wherein the covering member has a black body on at least a part of a main surface of the base material . The covering member according to any one of claims 6 to 9 , wherein the covering member has a thickness of 100 µm or less.   A method of evaluating expansion or contraction over time due to curing of the curable composition,
  Along with curing the curable composition contained in the containing member and having the covering member disposed on the surface, the covering member is continuously irradiated with laser light from a laser light source, and the position of the covering member is determined based on the reflected light. A measuring step of continuously measuring
  From the transition of the position measured in the measurement step, including an evaluation step of evaluating the expansion or contraction over time due to the curing of the curable composition,
  The coating member has a black body provided on at least a part of the main surface of the base material and the base material,
  The substrate has a reflectance of 50% or more to the laser light,
  The method wherein the coating member has a mass of 10 mg or less.   The method according to claim 11, wherein the covering member is arranged so as not to contact the receiving member.   The measuring step has an infrared amount measuring step of continuously measuring the amount of infrared radiation emitted from the coating member in a non-contact manner,
  The evaluation step includes a temperature evaluation step of evaluating a time-dependent temperature transition due to curing of the curable composition from a transition of the infrared ray amount measured in the infrared ray amount measurement step, according to claim 11 or 12. the method of.   The covering member used in the method according to any one of claims 11 to 13, comprising a rigid film having a mass of 10 mg or less.   The thermal conductivity of the base material is 70 Wm ^-1 K ^-1 The covering member according to claim 14, which is the above.   The covering member according to claim 15, wherein the base material is made of an inorganic material.   The covering member according to any one of claims 14 to 16, wherein the thickness is 100 µm or less.   14. Curing conditions of the curable composition, based on evaluation information of expansion or shrinkage of the curable composition over time caused by curing of the curable composition obtained by the method according to any one of claims 1 to 5 or 11 to 13. How to design.   The curable composition is designed based on the evaluation information of the time-dependent expansion or contraction caused by curing of the curable composition obtained by the method according to any one of claims 1 to 5 or 11 to 13. Method.

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