WO2010098010A1 - 活性エネルギー線硬化型樹脂組成物の硬化度評価方法、硬化度評価シート、および硬化度評価システム - Google Patents
活性エネルギー線硬化型樹脂組成物の硬化度評価方法、硬化度評価シート、および硬化度評価システム Download PDFInfo
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- WO2010098010A1 WO2010098010A1 PCT/JP2010/000362 JP2010000362W WO2010098010A1 WO 2010098010 A1 WO2010098010 A1 WO 2010098010A1 JP 2010000362 W JP2010000362 W JP 2010000362W WO 2010098010 A1 WO2010098010 A1 WO 2010098010A1
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- active energy
- resin composition
- energy ray
- curable resin
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
Definitions
- the present invention relates to a method for simply and accurately evaluating the curing degree of an active energy ray-curable resin composition that is cured by irradiation with active energy rays, a curing degree evaluation sheet for use in the method, and an active energy ray-curable type
- the present invention relates to a system for evaluating the degree of cure of a resin composition.
- the active energy ray-curable resin composition can be cured by active energy rays such as ultraviolet rays and electron beams, and from the viewpoint of transparency, fast curing property, fixability, etc., surface coating agent, adhesive, pressure-sensitive adhesive, It is used in many industrial fields as a sealant, paint, and the like.
- the active energy ray-curable resin composition is transparent or translucent, and it is difficult to visually determine the cured state of the active energy ray-curable resin composition and the presence or absence of quality abnormalities.
- the active energy ray-curable resin composition is used as an adhesive, there are many product claim cases that are caused by poor curing of the active energy ray-curable resin composition.
- the quality of the curing degree of the active energy ray-curable resin composition for each product should be inspected, but the reality is that there is no effective and realistic product quality inspection method.
- FT-IR method Fourier transform infrared spectroscopy
- Young's modulus a method for obtaining a change in hardness
- the FT-IR method is an analytical method in which the degree of cure is measured by irradiating infrared rays, measuring the amount of infrared absorption based on a specific functional group, and determining the conversion rate of the functional group from the increase or decrease.
- the degree of cure can be obtained from the change in the Young's modulus of the resin composition.
- Patent Document 1 discloses a method for visually confirming the presence or absence of curing of an ultraviolet curable epoxy resin by coloring a leuco dye.
- Patent Document 2 discloses a curable adhesive sheet that can easily confirm visually by color change whether or not the adhesive sheet has been reliably cured by light irradiation.
- Patent Document 3 discloses a method for producing a printed wiring board characterized by containing a leuco dye in a photosensitive electrodeposition paint. If a photosensitive resist is formed using a photosensitive electrodeposition paint containing a leuco dye, the resist can be colored, so that it can be visually confirmed that the resist is formed according to the pattern mask. It is disclosed that the defective rate in the manufacturing process can be reduced without impairing the photosensitivity of the resist.
- Patent Document 3 discloses that it can be confirmed that the resist is formed according to the pattern mask, but whether or not a desired pattern mask is formed is completely unrelated to the cured state. There is no problem regarding the evaluation of the cured state of the resist.
- the curing reactivity (hereinafter also referred to as the degree of curing) of the active energy ray-curable resin composition itself is quantified.
- the degree of curing the curing reactivity of the active energy ray-curable resin composition itself is quantified.
- Quantitative evaluation of the degree of cure of the active energy ray-curable resin composition is very important not only for ensuring product quality but also for optimizing the production process of the product.
- the FT-IR method and the method for obtaining the Young's modulus can quantitatively evaluate the degree of cure of the active energy ray-curable resin composition, there is a problem that the evaluation accuracy is low and has not been put into practical use. Yes.
- the present invention has been made in view of the above-mentioned problems, and its purpose is to provide an evaluation method capable of quantitatively evaluating the degree of cure of the active energy ray-curable resin composition easily and accurately, and the evaluation method. It is in providing the hardening degree confirmation sheet
- the present inventor has intensively studied an evaluation method capable of quantitatively evaluating the degree of curing of the active energy ray-curable resin composition simply, with high accuracy.
- the curing of the active energy ray-curable resin composition can be confirmed by color change by blending the active energy ray-curable resin composition with the leuco dye.
- the color value of the cured product of the active energy ray-curable resin composition correlates with the degree of cure, and by measuring the color value of the cured product of the active energy ray-curable resin composition
- the inventors have found that the degree of cure of the active energy ray-curable resin composition can be easily and accurately evaluated quantitatively, and the present invention has been completed.
- the method for evaluating the degree of cure of an active energy ray-curable resin composition is a method for evaluating the degree of cure of an active energy ray-curable resin composition, and includes the above-mentioned active energy ray-curable resin composition.
- An active energy ray curable resin composition comprising: irradiating an active energy ray; and a step of evaluating the degree of cure of the active energy ray curable resin composition based on the color of the active energy ray curable resin composition.
- the product is characterized by containing at least a radical polymerization compound, a leuco dye, and a radical polymerization initiator.
- the active energy includes at least a radical polymerization compound, a leuco dye, and a radical polymerization initiator. Since a linear curable resin composition is used, radicals generated from radical polymerization initiators upon irradiation with active energy rays cause radical polymerization compounds to undergo polymerization reactions (main chain reaction, crosslinking reaction, etc.), and active energy ray curable resins. The composition cures.
- the active energy ray-curable resin composition containing a leuco dye is colorless before irradiation with active energy rays, but the active energy ray-curable resin composition is irradiated with active energy rays, and radicals are generated from the radical polymerization initiator.
- an ionization reaction occurs in the contained leuco dye, and the leuco dye is colored blue. Since such a coloring reaction is an irreversible reaction, the irradiation history of the active energy ray can be recorded.
- the amount of generated radicals correlates with the degree of coloring of the leuco dye. That is, the degree of polymerization of the radical polymerization compound contained in the active energy ray-curable resin composition can be directly confirmed through the degree of coloring of the leuco dye.
- FIG. 1 is a diagram showing a change in the degree of coloring of an active energy ray-curable resin composition with respect to the length (seconds) of ultraviolet irradiation time when ultraviolet rays are irradiated as active energy rays.
- the coloring degree of the active energy ray-curable resin composition containing a leuco dye varies depending on the length of the ultraviolet irradiation time.
- 0.5 s to 150 s shown in FIG. 1 represents the ultraviolet irradiation time (seconds).
- the cured quality of a product can be easily evaluated.
- optimization of the manufacturing process such as examination of an efficient active energy ray irradiation method becomes easy.
- the conventional confirmation method has a problem that the evaluation accuracy is low, but according to the method for evaluating the degree of cure of the active energy ray-curable resin composition according to the present invention, as shown in the examples described later. Since the evaluation accuracy of the degree of curing is high, the reliability of the evaluation result is high.
- the degree of curing of the sheet is indicated by the transmittance of the sheet.
- the transmittance is low, and the evaluation accuracy is greatly reduced.
- the active energy ray-curable resin that becomes cloudy is used to evaluate the degree of cure from the color of the active energy ray-curable resin composition, for example, the color value using reflected light.
- the curing degree evaluation method according to the present invention is different from the method of evaluating by the transmittance described in Patent Document 2 in that the degree of curing is evaluated from the colorimetric value, and the obtained effect is very excellent. .
- the curing degree evaluation system is a curing degree of an active energy ray-curable resin composition containing at least a radical polymerization compound, a leuco dye, and a radical polymerization initiator.
- a cured state confirmation means for measuring and evaluating the degree of cure of the active energy ray-curable resin composition.
- the curing degree evaluation system can automatically evaluate the curing degree while curing the active energy ray-curable resin composition. Accordingly, it is possible to reduce defective curing products.
- the curing degree confirmation sheet according to the present invention is a curing degree confirmation sheet for evaluating the degree of curing of the active energy ray-curable resin composition, and includes at least radicals.
- a chemical solution containing a polymerization compound, a leuco dye, and a radical polymerization initiator is applied to a transparent resin material formed into a sheet shape.
- the curing degree confirmation sheet according to the present invention is obtained by applying a chemical solution containing at least a radical polymerization compound, a leuco dye, and a radical polymerization initiator to a transparent resin material formed into a sheet shape.
- the curing degree confirmation sheet is colored depending on the amount of radicals generated by irradiation with active energy rays. Therefore, if the degree of coloring of the curing degree confirmation sheet is examined, the activity irradiated with active energy rays at the same time
- the degree of cure of the energy beam curable resin composition can be a means for simple and rapid evaluation.
- the method for evaluating the degree of cure of an active energy ray-curable resin composition according to the present invention is a method for evaluating the degree of cure of an active energy ray-curable resin composition, comprising a cure degree confirmation sheet and an active energy ray according to the present invention. Including a step of simultaneously irradiating active energy rays to a coating portion of the curable resin composition, and a step of evaluating the degree of cure of the active energy ray curable resin composition based on the color of the cure degree confirmation sheet. It is a feature.
- the curing degree of the active energy ray-curable resin composition irradiated with the active energy rays at the same time is indirectly but easily and quickly evaluated. can do. Therefore, when evaluating the degree of cure of the active energy ray-curable resin composition, it is difficult to be restricted by the shape of the portion to which the active energy ray-curable resin composition is applied.
- the active energy ray-curable resin composition when the active energy ray-curable resin composition is cured in the presence of oxygen, since the generated radicals are captured by oxygen, only the surface layer that is in contact with the outside air does not cure the resin composition. There may be a case where surface tack due to uncured material occurs.
- the resin composition if the resin composition is cured in a state where the curing degree confirmation sheet is placed on the surface of the resin composition, there is no portion where the resin composition comes into contact with oxygen. Thereby, hardening inhibition of the resin composition by oxygen can be reduced, and surface tack due to uncured resin surface can be reduced.
- the method for evaluating the degree of cure of the active energy ray-curable resin composition according to the present invention includes the step of irradiating the active energy ray-curable resin composition with active energy rays and the color of the active energy ray-curable resin composition. And a step of evaluating the degree of cure of the active energy ray-curable resin composition, the active energy ray-curable resin composition includes at least a radical polymerization compound, a leuco dye, and a radical polymerization initiator. It is a feature. Therefore, there is an effect that the degree of cure of the active energy ray-curable resin composition can be easily and accurately evaluated quantitatively.
- the curing degree evaluation system includes an irradiation means for irradiating the active energy ray-curable resin composition with active energy rays, and the active energy ray-curable resin. It is characterized by comprising a cured state confirmation means for measuring a color at a site where the degree of curing of the composition is evaluated and evaluating the degree of curing of the active energy ray-curable resin composition.
- the curing degree evaluation system according to the present invention can automatically evaluate curing while curing the active energy ray-curable resin composition. Therefore, there is an effect that defective cured products can be reduced.
- the cure degree confirmation sheet according to the present invention is a cure degree confirmation sheet for evaluating the cure degree of the active energy ray-curable resin composition, and includes at least a radical polymerization compound, a leuco dye, and a radical polymerization initiator. It is characterized in that the chemical liquid is applied to a transparent resin material formed into a sheet shape. Therefore, if the degree of coloring of the curing degree confirmation sheet is investigated, the degree of curing of the active energy ray-curable resin composition irradiated with active energy rays at the same time is indirectly, but for simple and quick evaluation. There is an effect that it can be a means.
- FIG. (a) is typically the member which provided the drawing-in part in places other than the application object part, in order to evaluate the cure degree of an active energy ray hardening-type resin composition.
- FIG. (B) is a model of a member provided with a viewing window in a part of the member so that the degree of coloring of the portion to be coated can be confirmed in order to evaluate the degree of curing of the active energy ray-curable resin composition.
- a to B indicating a range indicates “A or more and B or less”.
- the method for evaluating the degree of cure of an active energy ray-curable resin composition according to the present invention is intended to evaluate the degree of cure of an active energy ray-curable resin composition.
- Such an active energy ray-curable resin composition is mainly liquid before irradiation with active energy rays, but is cured into a solid after irradiation with active energy rays.
- the term “active energy ray-curable resin composition” is used in a generic sense regardless of its state (liquid state before irradiation with active energy rays or solid state after irradiation with active energy rays).
- the active energy ray-curable resin composition to be evaluated by the method for evaluating the degree of cure according to the present invention can be used as, for example, a surface coating agent, an adhesive, a pressure-sensitive adhesive, a sealant, a paint,
- the evaluation object of the present invention is not limited to these.
- examples of the active energy ray used for curing the active energy ray-curable resin composition include ultraviolet rays and electron beams, but the present invention is not limited thereto.
- ultraviolet rays are more preferably used as active energy rays because they can be used at normal pressure.
- the method for evaluating the degree of cure of an active energy ray-curable resin composition according to the present invention includes: And a step of evaluating the degree of curing of the active energy ray-curable resin composition based on the color of the active energy ray-curable resin composition, the active energy ray-curable resin composition comprises: At least a radical polymerization compound, a leuco dye, and a radical polymerization initiator are included.
- the method for evaluating the degree of cure of an active energy ray-curable resin composition according to the present invention is activated simultaneously with the degree of cure confirmation sheet according to the present invention and the application portion of the active energy ray-curable resin composition.
- the active energy ray-curable resin composition used in the method for evaluating the degree of cure of the active energy ray-curable resin composition according to the present invention includes at least a radical polymerization compound, a leuco dye, and a radical polymerization initiator.
- the “radical polymerization compound” refers to a compound that can undergo addition polymerization by reacting with radicals generated from a radical polymerization initiator by irradiation of active energy rays, and may be a monomer, an oligomer, It may be a polymer.
- a monomer is also called a monomer, and points out the state used as a raw material in the case of synthesize
- the oligomer is also called a low polymer and refers to a state with a relatively low degree of polymerization of about 2 to 20 degrees of polymerization.
- the radical polymerization compound is not particularly limited, but is preferably selected from the group consisting of acrylates, methacrylates, vinyl ethers, and allyl ethers.
- acrylate examples include tetrahydrofurfuryl acrylate, stearyl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, dimethylaminoethyl acrylate, 2-hydroxy-3-phenoxypropyl metallate, ⁇ -carboxy-polycaprolactone monoacrylate.
- methacrylate examples include tetrahydrofurfuryl methacrylate, stearyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, ⁇ -carboxy-polycaprolactone monomethacrylate, Phthalic acid monohydroxyethyl methacrylate, hexahydrophthalic acid monohydroxyethyl methacrylate, bisphenol AEO modified dimethacrylate, tricyclodecane dimethylol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, pentaerythritol trimethallylate, pentaerythritol tetramethacrylate Rate, dimethylo It can be exemplified Le propane tetramethacrylate and the like.
- Examples of the “vinyl ether” include ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanediol divinyl ether, trimethylolpropane trivinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexane dimethanol monovinyl ether, Examples include cyclohexanediol monovinyl ether, 9-hydroxynonyl vinyl ether, and propylene glycol monovinyl ether.
- acrylic ether examples include trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin monoallyl ether, allyl glycidyl ether, triallyl isocyanurate, and the like.
- the above radical polymerization compounds may be used alone or in combination of two or more.
- the content of the radical polymerization compound is preferably 10% by weight to 99.5% by weight and more preferably 20% by weight to 99.5% by weight with respect to the total amount of the active energy ray-curable resin composition. Further preferred. When the content of the radical polymerization compound is 10% by weight or more, the active energy ray-curable resin composition can be sufficiently cured.
- the “leuco dye” is not particularly limited as long as it is a substance that is usually colorless or light colored and reacts with radicals generated from a radical polymerization initiator by irradiation with active energy rays, and is not particularly limited. There are also no particular restrictions on the color, but leuco crystal violet, leucoma calite green, leuco crystal violet lactone, leuco quinizarin, benzoyl leucomethylene blue, 2 '-(2-chloroanilino) -6'-(dibutylamino) fluorane, And 3 ′, 6′-bis (dimethylamino) -2- (4-nitrophenyl) spiro [isoindole-1,9′-xanthen] -3-one.
- leuco dyes may be used alone or in combination of two or more.
- the content of the leuco dye is preferably 0.001 to 10% by weight, more preferably 0.01 to 3% by weight, based on the total amount of the active energy ray-curable resin composition. preferable.
- the content of the leuco dye is 0.001% by weight or more, the coloring of the active energy ray-curable resin composition can be easily confirmed. Further, it is preferable that the content is 10% by weight or less because a change in color can be easily confirmed.
- the “radical polymerization initiator” includes a photopolymerization initiator and a thermal polymerization initiator.
- a photopolymerization initiator used for a photopolymerization (photocuring) reaction is used.
- the “photopolymerization initiator” is not particularly limited.
- 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide for example, trade name: Lucillin TPO, manufactured by BASF
- 2 -Hydroxy-2-methyl-1-phenyl-propen-1-one 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropen-1-one
- 2,4,6-trimethylbenzoyl -Diphenyl-phosphine oxide triphenylsulfonyl triflate
- 1-hydroxy-cyclohexyl leuphenyl ketone 2,2-dimethoxy-1,2-diphenylethane-1-one
- 2-methyl-1 [4- (methylthio) And phenyl] -2-morpholinopropan-1-one 2-4,6-trimethylbenzoyl-diphenyl-phosphine oxide
- the above radical polymerization initiators may be used alone or in combination of two or more.
- the content of the radical polymerization initiator is preferably 0.01% by weight to 10% by weight, and preferably 0.1% by weight to 5% by weight with respect to the total amount of the active energy ray-curable resin composition. Is more preferable.
- the content of the radical polymerization initiator is 0.01% by weight or more, the radical polymerization reaction can be sufficiently caused.
- the active energy ray-curable resin composition preferably further contains an inorganic filler in addition to the above-described radical polymerization compound, leuco dye, and radical polymerization initiator. Since the active energy ray-curable resin composition further containing an inorganic filler becomes cloudy, the use of such an active energy ray-curable resin composition makes it easy to confirm a color change. In addition, the rigidity of the active energy ray-curable resin composition is improved. Furthermore, there is an effect that shrinkage of the cured resin is reduced.
- the “inorganic filler” is not particularly limited, and examples thereof include silica and glass beads.
- inorganic fillers may be used alone or in combination of two or more.
- the content of the inorganic filler is preferably 5% by weight to 90% by weight and more preferably 30% by weight to 85% by weight with respect to the total amount of the active energy ray-curable resin composition.
- the content of the inorganic filler is 5% by weight or more, the obtained active energy ray-curable resin composition becomes cloudy and it becomes easy to confirm the coloring of the leuco dye.
- the rigidity of the active energy ray-curable resin composition is improved.
- shrinkage of the resin after curing is reduced.
- the content is 90% by weight or less, it is preferable because a change in color can be easily confirmed.
- the active energy ray-curable resin composition may contain an organic solvent, a silane coupling agent, and the like in addition to the above-described radical polymerization compound, leuco dye, radical polymerization initiator, and inorganic filler.
- the curing degree confirmation sheet according to the present invention is a sheet used for evaluating the curing degree of an active energy ray-curable resin composition that is cured by irradiation with active energy rays.
- the curing degree confirmation sheet is obtained by applying a chemical solution containing at least a radical polymerization compound, a leuco dye, and a radical polymerization initiator to a transparent resin material formed into a sheet shape.
- the “radical polymerization compound”, the “leuco dye”, and the “radical polymerization initiator” are as described in “1-1. Active energy ray-curable resin composition”.
- the chemical solution used for preparing the curing degree confirmation sheet may contain an organic solvent, a polymer, an inorganic filler, a silane coupling agent, etc. in addition to the radical polymerization compound, leuco dye, and radical polymerization initiator described above. Good.
- the curing degree confirmation sheet is used after being semi-cured, if the polymer used in the preparation of the curing degree confirmation sheet contains a polymer and an organic solvent, the curing degree confirmation sheet can be easily semi-cured. it can.
- the above “sheet shape” means a thin film shape and is synonymous with “film shape”.
- the “transparent resin material” is not particularly limited as long as it is a material made of a transparent resin.
- PET, PP, polyester, nylon and the like can be mentioned.
- the “transparent resin material molded into a sheet” refers to a material in which the above-described transparent resin is molded into a thin film.
- the “transparent resin material formed into a sheet” is not particularly limited as long as it can transmit active energy rays.
- a PET sheet, a PP sheet, a polyester sheet, a nylon sheet, or the like is used. Can do. Commercially available PET sheets, PP sheets, polyester sheets, nylon sheets, and the like can be used.
- the thickness of the transparent resin material is not particularly limited. For example, a transparent resin material having a thickness of 10 ⁇ m to 5 mm can be used. The thickness of the transparent resin material is preferably as uniform as possible.
- the method for applying the chemical solution is not particularly limited as long as it can be applied on the sheet with a uniform thickness.
- the chemical solution is applied with a uniform thickness using screen printing, gravure printing, spray coating dipping, or the like. can do.
- the thickness of the chemical solution to be applied is preferably 1 to 300 ⁇ m, more preferably 10 to 150 ⁇ m. If the thickness of the chemical
- the curing degree confirmation sheet may further semi-cur the applied chemical solution.
- “semi-cured” means that the fluidity of the resin composition is that the active energy ray-curable resin composition reacts to further active energy ray irradiation and leaves room for curing. Refers to almost none.
- the method of “semi-curing” for example, there is a method of heating a sheet coated with a chemical solution.
- the heating temperature is preferably 40 to 150 ° C, more preferably 40 to 80 ° C.
- a very small amount of active energy rays may be irradiated.
- the illuminance of the ultraviolet rays is preferably 0.5 to 20 mW, and the irradiation time is preferably 0.1 to 20 s. Even when active energy rays other than ultraviolet rays are used, irradiation conditions suitable for semi-curing may be appropriately studied and adopted.
- the curing degree evaluation method according to the present invention the curing degree of the active energy ray-curable resin composition is evaluated using the above-described active energy ray-curable resin composition or the curing degree confirmation sheet according to the present invention.
- the details of the curing degree evaluation method using the active energy ray-curable resin composition and the curing degree evaluation method using the curing degree confirmation sheet will be described below.
- (I) Curing degree evaluation method using active energy ray curable resin composition The degree of curing evaluation method using an active energy ray curable resin composition is “1-1. Active energy ray curable resin composition”. This is a method for evaluating the degree of curing based on the color of the resin composition using the described active energy ray-curable resin composition.
- the active energy ray-curable resin composition according to the present invention is colored, for example, by irradiation with ultraviolet rays. Therefore, if the degree of coloring of the active energy ray-curable resin composition is examined, the degree of curing of the active energy ray-curable resin composition can be easily and quickly evaluated.
- the degree of cure of the active energy ray-curable resin composition by comparing the color of the active energy ray-curable resin composition with a reference color.
- the “reference color” refers to color samples prepared in advance for various degrees of curing.
- the color sample and the activity By visually comparing the color of the energy ray-curable resin composition, the degree of cure of the resin composition can be easily evaluated.
- the correlation between the degree of cure and the color of the active energy ray curable resin composition may vary depending on the composition of the active energy ray curable resin composition, the curing conditions of the active energy ray curable resin composition, and the like.
- a more accurate degree of cure can be evaluated by preparing a color sample for the active energy ray-curable resin composition for which an evaluation of the degree of cure is required and comparing it with the color sample.
- the degree of cure of the active energy ray-curable resin composition by measuring the color value of the active energy ray-curable resin composition.
- the color system for measuring the color values is not particularly limited.
- the color values of these color systems can be measured using a curing state confirmation means, for example, a color difference meter.
- the degree of cure can be quantitatively calculated from the color value based on the calibration curve. According to this method, the degree of curing can be quantitatively evaluated with higher accuracy than visual color confirmation.
- the color values of X, Y, and Z after 0.5 seconds of irradiation with active energy rays are set to 0% curing degree, and the color values of X, Y, and Z after irradiation of active energy rays are 150 seconds.
- each degree of cure of 100% the curing of the active when color values of the energy ray irradiation t after seconds X was X t, the active energy ray irradiation t seconds after the active energy ray curable resin composition
- the degree evaluation formula can be expressed by the following formula (1).
- the degree of cure can be determined similarly.
- Curing degree (%)
- the degree of cure evaluation part of the active energy ray-curable resin composition is provided in addition to the application target part of the active energy ray-curable resin composition.
- the above-mentioned “curing degree evaluation part” refers to a part where the curing degree of the active energy ray-curable resin composition is evaluated based on the color.
- the “application target portion” refers to a portion to which the active energy ray-curable resin composition is applied in order to achieve the purpose.
- the “application target portion” refers to a portion to which the active energy ray-curable resin composition is applied for the purpose of bonding members together.
- the “application target portion” is applied with the active energy ray-curable resin composition for the purpose of sealing a part of the member. Refers to the part.
- the above-mentioned “object” refers to, for example, adhering members when the active energy ray-curable resin composition is used as an adhesive.
- the “application” It does not matter whether the “object” is achieved in the “target part”. That is, the present invention is intended to evaluate the degree of curing, and therefore, for example, when an active energy ray-curable resin composition is used as an adhesive, it does not matter whether a desired adhesive effect is actually obtained. .
- the degree of cure evaluation part of the active energy ray-curable resin composition is provided in a portion other than the application target portion of the active energy ray-curable resin composition” means that the active energy ray-curable resin is in a portion other than the purpose. It refers to the state where the composition is applied.
- FIG. (A) of FIG. 7 is a figure which shows one Embodiment of this invention, and in order to evaluate the cure degree of an active energy ray hardening-type resin composition, the member which provided the drawing-in part in places other than the application object part FIG.
- the drawing-in portion 21 is provided as a “curing degree evaluation portion” in a place other than the application target portion 22. Even when the application target part is indeterminate and it is difficult to accurately evaluate the degree of cure, the degree of cure of the active energy ray-curable resin composition is evaluated by providing the lead-in part 21 in the part that is easy to inspect. Can be easily performed.
- FIG. 7 is a diagram showing another embodiment of the present invention, and in order to evaluate the degree of curing of the active energy ray-curable resin composition, the degree of coloring of the application target portion inside is confirmed. It is a figure which shows typically the member which provided the observation window in a part of member so that it could.
- the “application target portion” refers to an adhesion portion between the member A and the member B. It is difficult to directly evaluate the color of the application target portion as shown in FIG. Therefore, by preparing the observation window 23 in the member A, it is possible to check the degree of coloring of the portion to be coated inside, so that the degree of cure of the active energy ray-curable resin composition can be easily evaluated. it can.
- the active energy ray-curable resin composition according to the present invention can be cured by irradiation with active energy rays. Moreover, it colors by active energy ray irradiation. Therefore, for example, when the active energy ray-curable resin composition according to the present invention is used as an adhesive, at least one of the members to be bonded transmits active energy rays such as quartz and organic materials. It is preferable that the material has a material that can be used (hereinafter referred to as “transmissible material”). Thereby, an active energy ray curable resin composition can be irradiated with an active energy ray through a permeable material, and the degree of coloring of the active energy ray curable resin composition can be easily confirmed. Although not shown, for example, when a transparent transmissive material is used as one of the members for adhesion, the coloring of the active energy ray-curable resin composition can be directly confirmed from the transparent member side.
- the transparent material examples include, but are not limited to, quartz, alkali glass, borosilicate glass, acrylic, polycarbonate, polyolefin, transparent polyimide, and the like.
- Curing degree evaluation method using a curing degree confirmation sheet includes a curing degree confirmation sheet and an active energy ray curable type described in “1-2. Curing degree confirmation sheet”. It is a method including the step of simultaneously irradiating active energy rays to the application part of the resin composition, and the step of evaluating the degree of curing of the active energy ray-curable resin composition based on the color of the curing degree confirmation sheet.
- the curing degree confirmation sheet according to the present invention is colored by irradiation with active energy rays. Therefore, if the degree of coloring of the curing degree confirmation sheet is examined, the curing degree of the active energy ray-curable resin composition not containing the leuco dye that has been irradiated with the active energy ray at the same time is indirectly, but simple, and It can be evaluated quickly.
- the place where the curing degree confirmation sheet is placed is irradiated with the active energy ray simultaneously on the curing degree confirmation sheet and the application portion of the active energy ray curable resin composition to be evaluated. It is not particularly limited as long as it can be performed.
- the curing degree confirmation sheet may be placed on or under the application portion of the active energy ray-curable resin composition to be evaluated. As shown in the examples to be described later, since the curing degree confirmation sheet colored by irradiation with active energy rays can transmit the active energy rays, the curing degree confirmation sheet is applied to the application portion of the active energy ray curable resin composition. Even when placed on top, there is little concern that the active energy ray-curable resin composition will inhibit curing.
- composition of the curing degree confirmation sheet and the composition of the active energy ray-curable resin composition that does not contain the leuco dye to be evaluated for the degree of curing are different, even if the active energy rays are irradiated under the same conditions, the state of the curing reaction
- a cure degree confirmation sheet used in such a degree of cure evaluation method except that it contains a leuco dye, an organic solvent, a polymer, It is preferable to use one having the same composition as the active energy ray-curable resin composition not containing the leuco dye to be evaluated for the degree of cure.
- a reference color For the method for comparing the color of the curing degree confirmation sheet and the reference color and the method for evaluating the curing degree of the active energy ray-curable resin composition, refer to “(i) Activity” in “1-3. Curing degree evaluation method”. It is as having mentioned above by the "curing degree evaluation method using an energy-beam curable resin composition.”
- the curing degree of the active energy ray-curable resin composition by measuring the color value of the curing degree confirmation sheet.
- the measuring method, and the evaluation method of the degree of curing “(i) Curing degree evaluation using an active energy ray-curable resin composition” in “1-3. Curing degree evaluation method” As described above in “Method”.
- the curing degree evaluation system irradiates an active energy ray-curable resin composition containing at least a radical polymerization compound, a leuco dye, and a radical polymerization initiator with active energy rays, and the active energy ray-curable resin composition
- This is a system that can automatically evaluate the degree of cure of the active energy ray-curable resin composition while curing the product.
- the curing degree evaluation system includes an irradiation means for irradiating an active energy ray-curable resin composition with active energy rays, and a color at a site for evaluating the degree of curing of the active energy ray-curable resin composition. And a cured state confirmation means for measuring and evaluating the degree of curing of the active energy ray-curable resin composition.
- the “irradiation means” is not particularly limited as long as the activation energy ray-curable resin composition can be irradiated with the activation energy ray.
- the “active energy rays” are not particularly limited, and examples thereof include ultraviolet rays and electron beams. Among them, it is more preferable to use ultraviolet rays because it can be used at normal pressure.
- the “cured state confirmation means” it is possible to measure the color at the site where the degree of cure of the activated energy ray-curable resin composition is evaluated and evaluate the degree of cure of the activated energy ray-curable resin composition. It is not particularly limited as much as possible.
- the color value of the activated energy ray-curable resin composition can be measured using a color difference meter.
- the “cured state confirmation means” may include an evaluation means for evaluating the degree of cure of the activated energy ray-curable resin composition based on the measured color.
- the curing degree evaluation system evaluates the degree of cure of the activated energy ray-curable resin composition by the light from the cured state confirmation means.
- Position control device for controlling the position so as to hit the part to be, a display device for determining pass / fail of the activated energy ray curable resin composition whose degree of cure has been evaluated, and classifying it as a pass product or a reject product A sorting device or the like may be further provided.
- FIG. 6 is a schematic diagram showing an outline of an example of the system 100 according to the present invention.
- the system 100 includes a light source (irradiation means) 10, a position control device (position control means) 11, a color difference meter (curing state confirmation means) 12, an inspection software (evaluation means) 13, a sorting device ( (Sorting means) 14 and stage 15, and an evaluation sample 16 to be inspected is placed on the stage 15.
- the curing degree evaluation system includes a light source (irradiation means) 10 that irradiates an activation energy ray-curable resin composition with activation energy rays.
- a light source irradiation means 10 that irradiates an activation energy ray-curable resin composition with activation energy rays.
- examples of the “light source” include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an LED lamp, a carbon arc lamp, and a xenon lamp. However, it is not limited to these.
- the amount of ultraviolet light irradiated from the light source is preferably 10 to 10,000 mW / cm 2 , although it varies depending on the component composition of the monomer composition.
- the wavelength range of the ultraviolet rays to be irradiated is not particularly limited, but is preferably 100 to 700 nm, and more preferably 200 to 500 nm.
- an electron beam may be used as the activation energy beam.
- the “light source” examples include a cockcroft type, a cockcroft Walton type, a pandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency type, and an electron curtain.
- Various electron beam accelerators such as molds can be used, but are not limited thereto.
- the position control device (position control means) 11 is a device for controlling the position so that light from the color difference meter (cured state confirmation means) 12 is applied to a portion where the degree of cure of the active energy ray-curable resin composition is evaluated. It is. Although not shown, the position control device (position control means) 11 recognizes a site for evaluating the degree of cure of the active energy ray-curable resin composition and the degree of cure of the active energy ray-curable resin composition. A moving means is provided for moving the evaluation sample 16 placed on the stage 15 in the horizontal direction so that light from the color difference meter 12 strikes the site to be evaluated.
- the color difference meter (cured state confirmation means) 12 is for measuring a color value at a site where the degree of cure of the active energy ray-curable resin composition is evaluated.
- the color difference meter (cured state confirmation unit) 12 applies, for example, ultraviolet light incident from above to the evaluation target portion of the evaluation sample 16 and measures the color value from the reflected light.
- the “cured state confirmation means” is not particularly limited as long as the color values can be measured.
- a spectrophotometer, a color luminance meter, and the like can be suitably used.
- the present invention is not limited to these.
- the inspection software (evaluation means) 13 evaluates the degree of cure of the active energy ray-curable resin composition based on the color value measured using the color difference meter 12 and transmits the result to the sorting device (sorting means) 14. Is for.
- the “evaluation means” for example, whether there is a significant difference between the color of the active energy ray-curable resin composition and the reference color or the color value of the active energy ray-curable resin composition is determined.
- Software with a function that determines that the value is within a predetermined reference value from the correlation between the degree of cure of the resin composition and the reference color can be mentioned, but is not limited to this. Absent.
- the sorting device (sorting means) 14 determines whether the active energy ray-curable resin composition whose degree of cure has been evaluated by the inspection software (evaluation means) 13 is acceptable, and determines whether the active energy ray-curable resin composition is acceptable or not. It is for classifying as an acceptable product. Specifically, it is preferable to have a function of sorting acceptable products and unacceptable products.
- the “sorting means” is not particularly limited as long as it has a function of sorting acceptable products and unacceptable products.
- the active energy ray-curable resin composition evaluated in the curing degree evaluation system according to the present invention includes the curing degree confirmation sheet according to the present invention.
- the curing degree confirmation sheet according to the present invention when using the above-mentioned degree of cure confirmation sheet in the degree of cure evaluation system, measure the color value of the degree of cure confirmation sheet by the cured state confirmation means, and determine the degree of cure of the degree of cure confirmation sheet based on the measured color value. evaluate.
- pass / fail of the cure degree from the evaluation result of the cure degree confirmation sheet, pass / fail of the cure degree of the active energy ray curable resin composition not containing the leuco dye irradiated with the active energy ray simultaneously with the cure degree confirmation sheet. Can be determined indirectly.
- the curing degree confirmation sheet according to the present invention is as described above in “1-2. Curing degree confirmation sheet”.
- the leuco dye is selected from leuco crystal violet, leucoma calite green, leuco crystal violet lactone, leuco quinizarin, benzoyl leucomethylene blue, 2 ′-(2-chloroanilino). ) -6 ′-(dibutylamino) fluorane, and 3 ′, 6′-bis (dimethylamino) -2- (4-nitrophenyl) spiro [isoindole-1,9′-xanthen] -3-one It is preferably at least one selected from the group.
- the radical polymerization compound is preferably at least one selected from the group consisting of acrylates, methacrylates, vinyl ethers, and allyl ethers.
- the curing time can be shortened.
- the color of the active energy ray-curable resin composition is compared with the reference color to cure the active energy ray-curable resin composition. It is preferable to evaluate the degree.
- the degree of cure of the active energy ray-curable resin composition is determined by measuring the color value of the active energy ray-curable resin composition. It is preferable to evaluate.
- the color specification value is a quantitative expression of color, and can be measured using, for example, a color difference meter.
- the degree of cure can be quantitatively determined. It becomes possible to grasp.
- the degree of cure can be quantified simply by measuring the color value of the active energy ray-curable resin composition, the quality of the product can be easily evaluated.
- the degree of cure evaluation part of the active energy ray-curable resin composition is other than the application target portion of the active energy ray-curable resin composition. It is preferable that it is provided.
- the part to be coated is indefinite, and it may be difficult to evaluate the degree of coloring of the active energy ray-curable resin composition. Therefore, for example, by creating a drawing-in part, that is, a part where the active energy ray-curable resin composition is applied in a place other than the application target part in a place other than the application target part, and providing a part that is easy to inspect, The degree of cure can be easily evaluated even with a regular sample.
- the active energy ray-curable resin composition preferably further contains an inorganic filler.
- the active energy ray-curable resin composition further containing an inorganic filler becomes cloudy as a whole, it is easier to visually confirm the color change of the active energy ray-curable resin composition than in the case of only the transparent resin composition. Thus, the degree of curing can be easily evaluated. In addition, the rigidity of the active energy ray-curable resin composition is improved. Furthermore, there is an effect that shrinkage of the cured resin is reduced.
- the curing degree confirmation sheet according to the present invention may be a sheet obtained by semi-curing the applied chemical.
- the degree of cure of the active energy ray-curable resin composition is evaluated by comparing the color of the cure degree confirmation sheet with a reference color. It is preferable.
- the degree of cure of the active energy ray-curable resin composition is evaluated by measuring the color value of the cure degree confirmation sheet. It is preferable.
- the curing degree of the active energy ray-curable resin composition irradiated with the active energy rays at the same time is indirectly but easily and quickly evaluated. can do.
- it is easy to measure the color value of the curing degree confirmation sheet it is easy to evaluate the curing degree of the active energy ray-curable resin composition. Therefore, when evaluating the degree of cure of the active energy ray-curable resin composition, it is difficult to be restricted by the shape of the portion to which the active energy ray-curable resin composition is applied.
- Example 1 ⁇ Evaluation of degree of cure by the method for measuring degree of cure according to the present invention> [1. Preparation of cured product of active energy ray-curable resin composition]
- an active energy ray curable resin composition a chemical solution prepared by mixing the compounds shown in Table 1 so as to be 100% by weight in total was prepared, and an appropriate amount of the chemical solution was applied onto a glass substrate, and then passed through a 50 ⁇ m thickness gauge. A glass slide was placed on the glass slide and irradiated with ultraviolet rays at 20 mW / cm 2 for 60 seconds using a mercury lamp. T. T. A cured product of a 50 ⁇ m active energy ray-curable resin composition was obtained.
- target sample About the cured product (hereinafter referred to as “target sample”) of the active energy ray-curable resin composition obtained in “1. Production of cured product of active energy ray-curable resin composition” and each of the comparative samples described above The color intensity was visually determined. The results are shown in Table 2. In Table 2, when the color of the comparison sample is darker than the color of the object sample, it is indicated as ⁇ , and when the color of the comparison sample is lighter than the color of the object sample, it is indicated as x.
- the active energy ray-curable resin composition is less colored than the target sample, even if it is visually judged, the active energy It was confirmed that the linear curability was inferior. That is, even if the difference in active energy ray irradiation time is about 20 seconds, it is possible to visually confirm the difference in the active energy ray cured state by comparing the degree of coloring of the active energy ray curable resin composition. It was possible. From this result, it was confirmed that defective products due to various factors occurring at the manufacturing site can be accurately identified.
- the degree of cure was evaluated from the obtained color values of X, Y, and Z.
- Curing degree evaluation method in “Mode for Carrying Out the Invention”, the color values of X, Y, and Z after 0.5 seconds of ultraviolet irradiation are set to 0 degree of curing, respectively. %, And X, Y, and Z color values after 150 seconds of UV irradiation are assumed to be 100% curing, respectively.
- the measurement accuracy of the method for measuring the degree of cure of the cured product of the active energy ray-curable resin composition according to the present invention was evaluated.
- an active energy ray curable resin composition a chemical solution prepared by mixing the compounds shown in Table 1 so as to be 100% by weight in total was prepared, and an appropriate amount of the chemical solution was applied onto a glass substrate, and then passed through a 50 ⁇ m thickness gauge. A glass slide was placed and ultraviolet irradiation was performed at 20 mW / cm 2 . Ultraviolet irradiation was performed for 10 seconds or 60 seconds to cure the active energy ray-curable resin composition, and Sample 1 for measurement accuracy evaluation was obtained.
- samples 2 to 5 for evaluation of measurement accuracy were obtained.
- the color values of X, Y, and Z were measured. Note that the standard deviation (3 ⁇ ) of samples 1 to 5 was obtained by multiplying the standard deviation of each of the X, Y, and Z measurement results for samples 1 to 5 by three.
- the degree of cure of the active energy ray-curable resin composition has not been evaluated, whereas the method for measuring the degree of cure of the active energy ray-curable resin composition according to the present invention is an active energy ray-curable resin. It was confirmed that the composition had sufficient accuracy for practical quality evaluation in the curing step of the composition.
- the reaction rate (A t ) of the curing reaction of the active energy ray-curable resin composition after t seconds of ultraviolet irradiation is a peak related to the C ⁇ O group of the cured product of the active energy ray-curable resin composition after t seconds of ultraviolet irradiation.
- C C peak area after t seconds). That is, it calculated
- the reaction rate (A 0.5 ) after 0.5 seconds of UV irradiation is 0% cure
- the reaction rate (A 150 ) after 150 seconds of UV irradiation is 100% cure.
- the degree of cure was evaluated. That is, when using the FT-IR method, when the reaction rate after UV irradiation t seconds was A t, the curing degree of the cured product of an active energy ray curable resin composition after UV irradiation t seconds evaluation formula Can be represented by the following formula (3).
- Curing degree (%)
- the result of the degree of cure obtained using the above formula (3) is shown in FIG.
- FIG. 3 is a graph showing the relationship between the ultraviolet irradiation time and the degree of cure measured using the FT-IR method.
- the degree of cure is calculated by setting the Young's modulus (E 0.5 ) of the cured product of the active energy ray-curable resin composition 0.5 seconds after UV irradiation to 0% cure and active energy ray curing 150 seconds after UV irradiation.
- the Young's modulus (E 150 ) of the cured product of the mold resin composition is assumed to be 100%.
- the Young's modulus of the cured product of the ultraviolet irradiation t seconds after the active energy ray curable resin composition and E t curing of the cured product of the radiation-curable resin composition after ultraviolet irradiation t seconds the following formula ( 4).
- Curing degree (%) (E t ⁇ E 0.5 ) / (E 150 ⁇ E 0.5 ) ⁇ 100 (4)
- the results calculated using the above equation (4) are shown in FIG.
- FIG. 4 is a graph showing the degree of cure of the cured product of the active energy ray-curable resin composition at each ultraviolet irradiation time.
- the degree of curing was changed according to the ultraviolet irradiation time, locally inconsistent results were obtained. This is due to the measurement error of the hardness meter and is difficult to improve.
- the method for measuring the Young's modulus is considered to be greatly inferior in accuracy.
- Example 2 An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that leucocalite green was used as the leuco dye and the ultraviolet irradiation time was set to an arbitrary irradiation time.
- Table 8 shows the composition of the prepared chemical solution. The degree of coloring of the active energy ray-curable resin composition of Example 2 in each ultraviolet irradiation time is shown in FIG.
- Example 3 An active energy ray-curable resin composition was produced in the same manner as in Example 1 except that leuco crystal violet lactone was used as the leuco dye and the ultraviolet irradiation time was set to an arbitrary irradiation time.
- Table 8 shows the composition of the prepared chemical solution. The degree of coloring of the active energy ray-curable resin composition of Example 3 in each ultraviolet irradiation time is shown in FIG.
- Example 4 An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that leucoquinizarin was used as the leuco dye and the ultraviolet irradiation time was set to an arbitrary irradiation time. Table 8 shows the composition of the prepared chemical solution. The degree of coloring of the active energy ray-curable resin composition of Example 4 during the ultraviolet irradiation time is shown in FIG.
- Example 5 An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that benzoylleucomethylene blue was used as the leuco dye and the ultraviolet irradiation time was set to an arbitrary irradiation time. Table 8 shows the composition of the prepared chemical solution. The degree of coloring of the active energy ray-curable resin composition of Example 5 at each ultraviolet irradiation time is shown in FIG.
- Example 6 The active energy ray curable type is the same as in Example 1 except that 2 ′-(2-chloroanilino) -6 ′-(dibutylamino) fluorane is used as the leuco dye and the ultraviolet irradiation time is set to an arbitrary irradiation time.
- a resin composition was prepared. Table 8 shows the composition of the prepared chemical solution. FIG. 8 shows the degree of coloring of the active energy ray-curable resin composition of Example 6 at each ultraviolet irradiation time.
- Example 7 3 ', 6'-bis (dimethylamino) -2- (4-nitrophenyl) spiro [isoindole-1,9'-xanthen] -3-one is used as the leuco dye, and the ultraviolet irradiation time is arbitrarily set.
- An active energy ray-curable resin composition was produced in the same manner as in Example 1 except that the time was used.
- Table 8 shows the composition of the prepared chemical solution. The degree of coloring of the active energy ray-curable resin composition of Example 7 at each ultraviolet irradiation time is shown in FIG. Note that 0.5 s to 150 s shown in FIG. 8 represents the ultraviolet irradiation time (seconds).
- Example 8 ⁇ Use of resin composition curing degree confirmation sheet> [1. Preparation of curing degree confirmation sheet] As a resin for preparing a curing degree confirmation sheet, a chemical solution in which the compounds shown in Table 9 were mixed so as to be 100% by weight in total was prepared.
- PET sheet model number: Tetron film SL type, manufactured by Teijin DuPont Films, Inc.
- screen printing is performed so that the resin has a thickness of 50 ⁇ m, followed by baking at 60 ° C. to form a sheet.
- a film for confirming the degree of cure was obtained. Then, it cut out to the size (3 cm x 3 cm) which is easy to use.
- FIG. 5 shows the arrangement of the curing degree confirmation sheet when the active energy ray-curable resin composition is irradiated with ultraviolet rays.
- a curing degree confirmation sheet 5 obtained by screen-printing a chemical solution 1 in which the compounds shown in Table 9 are mixed to a total of 100% by weight on a PET sheet 2 and baking at 60 ° C. was irradiated with ultraviolet rays on the active energy ray-curable resin composition 3 dropped on the slide glass 4. Thereafter, the curing degree confirmation sheet 5 discolored by ultraviolet irradiation is removed, and the color value of the curing degree confirmation sheet 5 is measured using a color difference meter (model number: spectrocolorimeter CM-3600d, manufactured by Konica Minolta Sensing Co., Ltd.). went.
- the active energy ray curable resin composition If the relationship between the UV irradiation amount, the color value of the curing degree confirmation sheet, and the curing degree of the cured product of the active energy ray curable resin composition is known in advance, the active energy ray curable resin composition The degree of cure of the cured product can be grasped. Further, according to this method, since it is not necessary to directly inspect the product, it is an extremely advantageous inspection method in terms of handling and throughput during inspection. Moreover, it is a method suitable for the goods which do not want to color the application part of an active energy ray hardening-type resin composition.
- the degree of cure of the active energy ray-curable resin composition can be evaluated easily, accurately and quantitatively, in a wide range of industries such as various electronic equipment industries using the active energy ray-curable resin composition. Can be used for product quality evaluation.
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Abstract
Description
本発明にかかる活性エネルギー線硬化型樹脂組成物の硬化度評価方法は、活性エネルギー線硬化型樹脂組成物の硬化度を評価することを目的としている。かかる活性エネルギー線硬化型樹脂組成物は、活性エネルギー線の照射前においては主に液体である一方、活性エネルギー線の照射後においては固体に硬化する。本明細書において、「活性エネルギー線硬化型樹脂組成物」とは、その状態(活性エネルギー線照射前の液体状態、もしくは活性エネルギー線照射後における固体状態)にかかわらず総称的な意味で用いる。また、本発明にかかる硬化度評価方法の評価対象となる活性エネルギー線硬化型樹脂組成物は、例えば、表面コート剤、接着剤、粘着剤、封止剤、塗料等として用いることができるが、本発明の評価対象はこれらに限定されない。
本発明にかかる活性エネルギー線硬化型樹脂組成物の硬化度評価方法で用いられる活性エネルギー線硬化型樹脂組成物は、少なくとも、ラジカル重合化合物、ロイコ染料、およびラジカル重合開始剤を含む。
本発明にかかる硬化度確認シートは、活性エネルギー線照射によって硬化する活性エネルギー線硬化型樹脂組成物の硬化度を評価するために用いられるシートである。当該硬化度確認シートは、少なくとも、ラジカル重合化合物、ロイコ染料、およびラジカル重合開始剤を含む薬液が、シート状に成形された透明樹脂材料に塗布されてなる。
本発明にかかる硬化度評価方法では、上述した活性エネルギー線硬化型樹脂組成物、または本発明にかかる硬化度確認シートを用いて活性エネルギー線硬化型樹脂組成物の硬化度の評価を行う。以下に、活性エネルギー線硬化型樹脂組成物を用いた硬化度評価方法、および硬化度確認シートを用いた硬化度評価方法について詳細を説明する。
活性エネルギー線硬化型樹脂組成物を用いた硬化度評価方法は、「1-1.活性エネルギー線硬化型樹脂組成物」で説明した活性エネルギー線硬化型樹脂組成物を用い、当該樹脂組成物の色に基づき硬化度を評価する方法である。本発明にかかる活性エネルギー線硬化型樹脂組成物は、例えば、紫外線の照射により着色される。よって、上記活性エネルギー線硬化型樹脂組成物の着色の程度を調べれば、活性エネルギー線硬化型樹脂組成物の硬化の程度を簡便、且つ迅速に評価することができる。
硬化度(%)=|(Xt-X0.5)/(X150-X0.5)|×100 ・・・ (1)
さらに別の一実施形態において、活性エネルギー線硬化型樹脂組成物の硬化度評価部分が、活性エネルギー線硬化型樹脂組成物の塗布対象部分以外に設けてあることが好ましい。
硬化度確認シートを用いた硬化度評価方法は、「1-2.硬化度確認シート」で説明した硬化度確認シートと活性エネルギー線硬化型樹脂組成物の塗布部分とに同時に活性エネルギー線照射を行う工程と、上記硬化度確認シートの色に基づき上記活性エネルギー線硬化型樹脂組成物の硬化度を評価する工程とを含む方法である。
本発明にかかる硬化度評価システムは、少なくとも、ラジカル重合化合物、ロイコ染料、およびラジカル重合開始剤を含む活性エネルギー線硬化型樹脂組成物に活性エネルギー線を照射し、当該活性エネルギー線硬化型樹脂組成物の硬化を行いつつ、活性エネルギー線硬化型樹脂組成物の硬化度を自動的に評価することができるシステムである。
本発明にかかる硬化度確認シートについては、上記「1-2.硬化度確認シート」で説明したとおりである。
<本発明にかかる硬化度測定法による硬化度の評価>
〔1.活性エネルギー線硬化型樹脂組成物の硬化物の作製〕
活性エネルギー線硬化型樹脂組成物として、表1に示す化合物を合計100重量%となるように混合した薬液を調製し、当該薬液をガラス基板上に適量を塗布した後に、50μmのシックネスゲージを介してスライドガラスを置き、水銀灯を用いて20mW/cm2で60秒間、紫外線照射を行い、スライドガラス上にF.T.50μmの活性エネルギー線硬化型樹脂組成物の硬化物を得た。
(2-1.硬化状態の目視確認)
(目視確認方法)
活性エネルギー線照射時間を、各5秒、40秒、60秒、80秒とした以外は、「1.活性エネルギー線硬化型樹脂組成物の硬化物の作製」と同様の方法で目視確認用の比較サンプルを作製した。
(表色値測定方法)
「1.活性エネルギー線硬化型樹脂組成物の硬化物の作製」で得られた活性エネルギー線硬化型樹脂組成物の硬化物について、色差計(型番:分光測色計CM-3600d、コニカミノルタセンシング株式会社製)を用い、反射測定モードでxyz表色系のX、Y、およびZの各表色値を測定した。表3に各紫外線照射時間における活性エネルギー線硬化型樹脂組成物の硬化物のX、Y、およびZの各表色値を示す。
硬化度(%)=|(Xt-X0.5)/(X150-X0.5)|×100 ・・・ (1)
表3に示す各紫外線照射時間におけるX、Y、およびZの硬化度を算出した。結果を図2に示す。図2は、紫外線照射時間とX、Y、およびZの各表色値から算出した硬化度との関係を示すグラフである。
次に、本発明にかかる活性エネルギー線硬化型樹脂組成物の硬化物の硬化度の測定方法の測定精度について評価を行った。活性エネルギー線硬化型樹脂組成物として、表1に示す化合物を合計100重量%となるように混合した薬液を調製し、当該薬液をガラス基板上に適量を塗布した後に、50μmのシックネスゲージを介してスライドガラスを置いて、20mW/cm2で紫外線照射を行った。10秒間または60秒間紫外線照射を行い、活性エネルギー線硬化型樹脂組成物を硬化させ、測定精度評価用のサンプル1を得た。同様にして測定精度評価用のサンプル2~5を得た。得られた活性エネルギー線硬化型樹脂組成物のサンプル1~5について、X、Y、およびZの各表色値を測定した。なお、サンプル1~5の標準偏差(3σ)は、サンプル1~5についてのX,Y,Zそれぞれの測定結果の標準偏差を3倍することによって求めた。
<FT-IR法による硬化度の評価>
〔1.活性エネルギー線硬化型樹脂組成物の硬化物の作製〕
実施例1と同様の方法により活性エネルギー線硬化型樹脂組成物の硬化物を作製した。
(FT-IR法)
「1.活性エネルギー線硬化型樹脂組成物の硬化物の作製」で得られた活性エネルギー線硬化型樹脂組成物の硬化物について、FT-IR法を用いて活性エネルギー線硬化型樹脂組成物の硬化度の評価を行った。本実施例においては、紫外線照射0秒後の未硬化の活性エネルギー線硬化型樹脂組成物および紫外線照射時間をそれぞれ変えて硬化させて得られた硬化物について、ゴールデンゲートダイヤモンドATRを付属したFT-IR(型番:system2000、パーキンエルマー社製)により、C=C基由来の吸光度ピーク(1630cm-1)とC=O基由来の吸光度ピーク(1730cm-1)とについて、ピーク面積を測定した。
反応率(At)=t秒後のC=Cピーク面積/t秒後のC=Oピーク面積 ・・・ (2)
次に、紫外線照射0.5秒後の反応率(A0.5)の値を硬化度0%、紫外線照射150秒後の反応率(A150)の値を硬化度100%と仮定して、硬化度を評価した。つまり、FT-IR法を用いた場合、紫外線照射t秒後の反応率がAtであった場合、紫外線照射t秒後の活性エネルギー線硬化型樹脂組成物の硬化物の硬化度の評価式は、下記式(3)で表すことができる。
硬化度(%)=|{At-(A150-A0.5)}/(A150-A0.5)|×100 ・・・ (3)
上記式(3)を用いて得られた硬化度の結果を図3に示す。図3は、紫外線照射時間とFT-IR法を用いて測定した硬化度の関係を示すグラフである。
次に、実施例1と同様に評価精度の確認を行った。紫外線照射時間が10秒、または60秒の測定精度評価用のサンプル1~5をそれぞれ作製し、上記式(3)を用いて硬化度の評価を行った。硬化度の算出のために必要なA150およびA0は、硬化度評価のデータを用いた。サンプル1~5の硬化度を表6に示す。
<ヤング率測定による硬化度の評価>
比較例1で行ったFT-IR法と同様に一般的な活性エネルギー線硬化型樹脂組成物の硬化度の評価方法として、ヤング率の大きさによって硬化物の硬化度を評価した。
実施例1と同様の方法により活性エネルギー線硬化型樹脂組成物の硬化物を作製した。
(ヤング率測定法)
「1.活性エネルギー線硬化型樹脂組成物の硬化物の作製」で得られた活性エネルギー線硬化型樹脂組成物の硬化物について、ヤング率を測定した。当該ヤング率は、従来公知の方法を用いて測定することができる(「新UV・EB硬化技術と応用展開,p.55,株式会社シーエムシー」の記載を参照)。本実施例においては、フィッシャー硬度計(型番:WIN-HCU、株式会社フィッシャーインストルメンツ製)を用いて、ビッカース圧子にて、荷重増加モードで、速度1mN/sで針入および引き抜きを行うことにより、活性エネルギー線硬化型樹脂組成物の硬化物のヤング率の測定を行った。
硬化度(%)=(Et-E0.5)/(E150-E0.5)×100 ・・・ (4)
上記式(4)を用いて算出した結果を図4に示す。図4は、各紫外線照射時間における活性エネルギー線硬化型樹脂組成物の硬化物の硬化度示すグラフである。
次に、実施例1と同様に評価精度の確認を行った。紫外線照射時間が10秒、または60秒の測定精度評価用のサンプル1~5をそれぞれ作製し、上記式(4)を用いて硬化度の評価を行った。硬化度の算出のために必要なE150およびE0は、硬化度評価のデータを用いた。サンプル1~5の硬化度を表7に示す。
ロイコ染料として、ロイコマカライトグリーンを用い、紫外線照射時間を任意の照射時間とした以外は、実施例1と同様の方法により活性エネルギー線硬化型樹脂組成物を作製した。調製した薬液の組成を表8に示す。各紫外線照射時間における実施例2の活性エネルギー線硬化型樹脂組成物の着色の程度を図8に示す。
ロイコ染料として、ロイコクリスタルバイオレットラクトンを、紫外線照射時間を任意の照射時間とした以外は、実施例1と同様の方法により活性エネルギー線硬化型樹脂組成物を作製した。調製した薬液の組成を表8に示す。各紫外線照射時間における実施例3の活性エネルギー線硬化型樹脂組成物の着色の程度を図8に示す。
ロイコ染料として、ロイコキニザリンを、紫外線照射時間を任意の照射時間とした以外は、実施例1と同様の方法により活性エネルギー線硬化型樹脂組成物を作製した。調製した薬液の組成を表8に示す。紫外線照射時間における実施例4の活性エネルギー線硬化型樹脂組成物の着色の程度を図8に示す。
ロイコ染料として、ベンゾイルロイコメチレンブルーを、紫外線照射時間を任意の照射時間とした以外は、実施例1と同様の方法により活性エネルギー線硬化型樹脂組成物を作製した。調製した薬液の組成を表8に示す。各紫外線照射時間における実施例5の活性エネルギー線硬化型樹脂組成物の着色の程度を図8に示す。
ロイコ染料として、2’-(2-クロロアニリノ)-6’-(ジブチルアミノ)フルオランを用い、紫外線照射時間を任意の照射時間とした以外は、実施例1と同様の方法により活性エネルギー線硬化型樹脂組成物を作製した。調製した薬液の組成を表8に示す。各紫外線照射時間における実施例6の活性エネルギー線硬化型樹脂組成物の着色の程度を図8に示す。
ロイコ染料として、3’,6’-ビス(ジメチルアミノ)-2-(4-ニトロフェニル)スピロ[イソインドール-1,9’-キサンテン]-3-オンを用い、紫外線照射時間を任意の照射時間とした以外は、実施例1と同様の方法により活性エネルギー線硬化型樹脂組成物を作製した。調製した薬液の組成を表8に示す。各紫外線照射時間における実施例7の活性エネルギー線硬化型樹脂組成物の着色の程度を図8に示す。なお、図8に記載されている0.5s~150sは紫外線照射時間(秒)を表す。
<樹脂組成物硬化度確認シートの利用>
〔1.硬化度確認シートの作製〕
硬化度確認シート作製用の樹脂として、表9に示す化合物を合計100重量%となるように混合した薬液を調製した。
硬化度確認シートを用いた活性エネルギー線硬化度評価方法の概略を図5に示す。図5は、活性エネルギー線硬化型樹脂組成物に紫外線照射をする際の上記硬化度確認シートの配置を表す。
2 PETシート
3 活性エネルギー線硬化型樹脂組成物
5 硬化度確認シート
10 光源(照射手段)
11 位置制御装置(位置制御手段)
12 色差計(硬化状態確認手段)
13 検査ソフト(評価手段)
14 仕分け装置(分別手段)
21 引き込み部
22 塗布対象部分
23 のぞき窓
100 硬化度評価システム
Claims (13)
- 活性エネルギー線硬化型樹脂組成物の硬化度を評価する方法であって、
上記活性エネルギー線硬化型樹脂組成物に活性エネルギー線を照射する工程と、
上記活性エネルギー線硬化型樹脂組成物の色に基づき当該活性エネルギー線硬化型樹脂組成物の硬化度を評価する工程とを含み、
上記活性エネルギー線硬化型樹脂組成物は、少なくとも、ラジカル重合化合物、ロイコ染料、およびラジカル重合開始剤を含むことを特徴とする方法。 - 上記ロイコ染料は、ロイコクリスタルバイオレット、ロイコマカライトグリーン、ロイコクリスタルバイオレットラクトン、ロイコキニザリン、ベンゾイルロイコメチレンブルー、2’-(2-クロロアニリノ)-6’-(ジブチルアミノ)フルオラン、および3’,6’-ビス(ジメチルアミノ)-2-(4-ニトロフェニル)スピロ[イソインドール-1,9’-キサンテン]-3-オンからなる群より選ばれる1種以上であることを特徴とする請求項1に記載の方法。
- 上記ラジカル重合化合物は、アクリレート、メタクリレート、ビニルエーテル、およびアリルエーテルからなる群より選ばれる1種以上であることを特徴とする請求項1に記載の方法。
- 上記活性エネルギー線硬化型樹脂組成物の色と基準色とを比較することにより当該活性エネルギー線硬化型樹脂組成物の硬化度を評価することを特徴とする請求項1に記載の方法。
- 上記活性エネルギー線硬化型樹脂組成物の表色値を測定することにより当該活性エネルギー線硬化型樹脂組成物の硬化度を評価することを特徴とする請求項1に記載の方法。
- 上記活性エネルギー線硬化型樹脂組成物の硬化度評価部分が、上記活性エネルギー線硬化型樹脂組成物の塗布対象部分以外に設けてあることを特徴とする、請求項1に記載の方法。
- 上記活性エネルギー線硬化型樹脂組成物は、さらに無機充填剤を含むことを特徴とする請求項1に記載の方法。
- 少なくとも、ラジカル重合化合物、ロイコ染料、およびラジカル重合開始剤を含む活性エネルギー線硬化型樹脂組成物の硬化度を評価する硬化度評価システムであって、
上記活性エネルギー線硬化型樹脂組成物に活性エネルギー線を照射する照射手段と、
上記活性エネルギー線硬化型樹脂組成物の硬化度を評価する部位における色を測定し、当該活性エネルギー線硬化型樹脂組成物の硬化度を評価する硬化状態確認手段とを備えることを特徴とする硬化度評価システム。 - 活性エネルギー線硬化型樹脂組成物の硬化度を評価するための硬化度確認シートであって、
少なくとも、ラジカル重合化合物、ロイコ染料、およびラジカル重合開始剤を含む薬液が、シート状に成形された透明樹脂材料に塗布されてなることを特徴とする硬化度確認シート。 - さらに、塗布された上記薬液を半硬化させてなることを特徴とする請求項9に記載の硬化度確認シート。
- 活性エネルギー線硬化型樹脂組成物の硬化度を評価する方法であって、
請求項9に記載の硬化度確認シートと活性エネルギー線硬化型樹脂組成物の塗布部分とに同時に活性エネルギー線照射を行う工程と、
上記硬化度確認シートの色に基づき上記活性エネルギー線硬化型樹脂組成物の硬化度を評価する工程とを含むことを特徴とする方法。 - 上記硬化度確認シートの色と基準色とを比較することにより上記活性エネルギー線硬化型樹脂組成物の硬化度を評価することを特徴とする請求項11に記載の方法。
- 上記硬化度確認シートの表色値を測定することにより上記活性エネルギー線硬化型樹脂組成物の硬化度を評価することを特徴とする請求項11に記載の方法。
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