WO2023062938A1 - 樹脂組成物の吐出方法、電子部品の製造方法、及び電子部品 - Google Patents
樹脂組成物の吐出方法、電子部品の製造方法、及び電子部品 Download PDFInfo
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- WO2023062938A1 WO2023062938A1 PCT/JP2022/031256 JP2022031256W WO2023062938A1 WO 2023062938 A1 WO2023062938 A1 WO 2023062938A1 JP 2022031256 W JP2022031256 W JP 2022031256W WO 2023062938 A1 WO2023062938 A1 WO 2023062938A1
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- methacrylate
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- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Definitions
- the present invention relates to a resin composition ejection method, an electronic component manufacturing method, and an electronic component. Further, the present invention relates to a resin composition discharge method capable of effectively suppressing curing of the resin composition in a jet dispenser, an electronic component manufacturing method, and an electronic component manufactured by the manufacturing method.
- UV and/or thermosetting adhesives for electronic parts In the process of applying UV and/or thermosetting adhesives for electronic parts, air dispensers are the mainstream, but there are challenges in reducing minute areas, minute applications, and production takt time.
- UV and/or thermosetting adhesives for electronic parts may be collectively referred to simply as "adhesives for electronic parts.”
- thermosetting adhesives tend to gel locally due to frictional heat generated inside the jet dispenser, so it is difficult to apply highly reactive adhesives such as (meth)acrylate-radical adhesives continuously and stably. became a serious problem.
- Gelation refers to the initiation of a polymer polymerization process, formation of a three-dimensional network structure, and increased viscosity and elasticity.
- Patent Document 1 discloses a resin composition that uses acrylate and thiol and can be applied by jet dispensing, but does not disclose any cases that were actually considered. Moreover, Patent Document 1 does not disclose a specific configuration of the jet dispenser (jet dispensing device) to be used, such as the material of the needle for discharging the resin composition.
- jet dispenseability the coating performance by jet dispensing may be referred to as "jet dispenseability”.
- the present invention has been made in view of such problems of the prior art.
- the present invention provides a resin composition discharge method capable of effectively suppressing curing of the resin composition in a jet dispenser.
- the present invention also provides a method for manufacturing an electronic component using the method for discharging the resin composition described above, and an electronic component manufactured by the manufacturing method.
- the following resin composition ejection method, electronic component manufacturing method, and electronic component are provided.
- a method for discharging a resin composition using a jet dispenser wherein the resin composition is discharged from a nozzle of the jet dispenser, In the jet dispenser, a member that collides with the nozzle when the resin composition is discharged is made of metal, and A method for discharging a resin composition, wherein the resin composition contains (A) a methacrylate compound and (B) a radical polymerization initiator.
- the resin composition contains both the (C1) polyfunctional thiol compound and the (C2) acrylate compound as the (C) component, and the total number of thiol groups of the (C1) polyfunctional thiol compound ,
- the resin composition contains only the (C1) polyfunctional thiol compound as the (C) component, and the ratio of the (A) methacrylate compound to the total number of thiol groups of the (C1) polyfunctional thiol compound
- the resin composition ejection method of the present invention is a resin composition ejection method in which a jet dispenser is used and the resin composition is ejected from the nozzle of the jet dispenser. According to the method for discharging the resin composition of the present invention, the resin composition can be continuously applied in a very small amount to a very small area using a jet dispenser.
- the method for discharging the resin composition of the present invention may be simply referred to as "discharging method".
- the resin composition containing (A) the methacrylate compound since the resin composition containing (A) the methacrylate compound is used, gelling of the resin composition inside the jet dispenser can be effectively suppressed. Therefore, even when frictional heat or the like is generated inside the jet dispenser, local gelation of the resin composition is unlikely to occur, workability and stability are high, and extremely excellent jet dispensing properties can be achieved. can.
- the ejection method of the present invention is used for bonding members constituting a camera module, and is mainly used for temporary fixing (for example, active alignment process) using curing by UV irradiation and applying adhesive for fixing. It is preferably used for the step of Moreover, it is also applicable to a process of applying a thermally cured adhesive without irradiating UV.
- a method for manufacturing an electronic component according to the present invention is a method for manufacturing an electronic component using the discharge method according to the present invention. can be done. Therefore, the method of manufacturing an electronic component according to the present invention is extremely effective as a method of manufacturing a small electronic component that requires adhesion. Further, the electronic component of the present invention is an electronic component manufactured by the manufacturing method described above, and good adhesion between the electronic members is realized.
- jet dispenser It is a cross-sectional schematic diagram of an example of a jet dispensing apparatus (jet dispenser).
- FIG. 1 is a schematic cross-sectional view of an example of a jet dispensing device (jet dispenser 50).
- the jet dispenser 50 includes a needle 52 capable of reciprocating motion like a piston, a seal 54 (sealing member) for preventing the resin composition 20 from leaking to the outside even when the needle 52 reciprocates, and a resin composition. and a nozzle 56 for jetting 20 .
- a syringe (not shown) filled with the resin composition is pushed out by air pressure and the needle 52 reciprocates with the length of the stroke S, whereby the resin composition 20 is It is supplied to the chamber 58 in the jet dispenser 50 and jet dispensed from the nozzle 56 .
- the nozzle 56 has an inner diameter of 20 to 300 ⁇ m.
- the resin composition 20 jet-dispensed from the nozzle 56 is supplied to a predetermined target.
- the reciprocating needle 52 collides with the nozzle 56 .
- the material of the needle 52 which is a member that collides with the nozzle 56 when the resin composition 20 is ejected, is made of metal.
- the needle 52 is called by different names depending on the device manufacturer, and is sometimes called a tappet, a poppet, or a rod.
- the material of the needle 52 that collides with the nozzle 56 is not particularly limited as long as it is metal.
- the material of the needle 52 is preferably cemented carbide, and in particular, tungsten carbide can be mentioned as a suitable example.
- the use of (A) a methacrylate compound as the resin composition 20 is also one of the main configurations.
- curing of the resin composition 20 inside the jet dispenser 50 can be effectively suppressed.
- workability and stability are high, and extremely excellent continuous jet dispensing can be performed.
- sexuality For example, when the resin composition 20 is applied by the jet dispenser 50, impact and heat are applied to the resin composition 20 supplied to the nozzle 56. Therefore, if the reactivity of the resin composition 20 is too high, the resin composition 20 It gels and becomes difficult to discharge.
- a range indicated by reference numeral 61 in FIG. 1B is a sliding portion 61 in which the needle 52 slides against the seal 54 as the needle 52 reciprocates. It depends on the resin composition 20 .
- a range indicated by reference numeral 62 in FIG. 1B is a collision portion 62 where the tip of the needle 52 collides with the nozzle 56 as the needle 52 reciprocates. It depends on the resin composition 20 .
- the resin composition 20 may contain (A) a methacrylate compound and (B) a radical polymerization initiator.
- the resin composition 20 may contain no acrylate compound or may contain an acrylate compound. Since the resin composition 20 contains (A) a methacrylate compound, it is excellent in workability and stability even if it contains, for example, a polyfunctional thiol compound that promotes reaction.
- the resin composition 20 used in the ejection method of the present embodiment contains an acrylate compound generally used in conventional (meth)acrylate-radical resin compositions as an optional component. As described above, by using the resin composition 20 containing (A) a methacrylate compound as an essential component, stable ejection by jet dispensing becomes possible.
- the methacrylate compound (A) may be referred to as component (A)
- the radical polymerization initiator (B) may be referred to as component (B).
- the resin composition 20 can be applied in a very small amount to a very small area with the jet dispenser 50 .
- a discharge method is used for bonding members constituting a camera module, and is mainly used for temporary fixing (for example, an active alignment process) using curing by UV irradiation and a process of applying an adhesive for fixing. It is preferably used for Moreover, it is also applicable to a process of applying a thermally cured adhesive without irradiating UV.
- the adhesive is applied by jet dispensing, impact and heat are applied to the adhesive supplied to the nozzle. Therefore, if the resin composition used as the adhesive has good reactivity, the adhesive gels and cannot be discharged.
- jet dispensing properties are improved by controlling this reactivity.
- the ejection method of this embodiment can be applied to adhesives that are only heat-cured without UV irradiation, so it can be suitably applied to, for example, engineering plastics.
- Resin composition 20 further contains at least one of (C1) polyfunctional thiol compound and (C2) acrylate compound as component (C) in addition to (A) methacrylate compound and (B) radical polymerization initiator.
- the polyfunctional thiol compound (C1) may be referred to as the (C1) component
- the acrylate compound (C2) may be referred to as the (C2) component.
- the resin composition 20 may also contain other components such as (D) an anionic polymerization initiator, (E) a polymerization inhibitor, (F) a filler, and (G) a black pigment.
- the components described above may also be referred to as components (D) to (G) as appropriate.
- Each component of the resin composition 20 will be described in more detail below.
- Component is a methacrylate compound.
- Component (A) is not particularly limited as long as it has a methacryloyl group.
- the number of functional groups that is, the number of methacryloyl groups
- the reactivity of the resin composition can be controlled, and gelation of the resin composition inside the jet dispenser can be made difficult to occur.
- the methacrylate compound preferably has a functional group equivalent weight of 100 or more and 500 or less, more preferably 100 or more and 400 or less, and 100 or more and 250 or less, from the viewpoint of reactivity, dispersibility and workability. is more preferred.
- the number of functional groups in one molecule is preferably 1-6, more preferably 1-4, and even more preferably 2 or 3.
- the component (A) preferably contains a benzene ring in the molecule for the purpose of providing high heat resistance and high reliability to the cured physical properties of the resin composition.
- the resin composition does not contain a benzene ring in order to make the physical properties of the resin composition after curing low in elasticity.
- methacrylate compounds include 2-hydroxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 4-hydroxybutyl methacrylate, cyclohexane-1,4-dimethanol monomethacrylate, tetrahydro furfuryl methacrylate, phenoxyethyl methacrylate, phenyl polyethoxy methacrylate, 2-hydroxy-3-phenyloxypropyl methacrylate, o-phenylphenol monoethoxy methacrylate, o-phenylphenol polyethoxy methacrylate, p-cumylphenoxyethyl methacrylate, isobonyl methacrylate, tribromophenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, 1,4-butanediol dimethacrylate, 1,6
- ((B) component) (B) Component is a radical polymerization initiator. Since the resin composition contains a radical polymerization initiator as the component (B), the resin composition can be cured by short-time heating or UV irradiation.
- the radical polymerization initiator of component (B) may be a thermal radical polymerization initiator alone, a photoradical polymerization initiator alone, or a combination of these two.
- the (B) component radical polymerization initiator is more preferably a radical photopolymerization initiator.
- radical polymerization initiator that can be used in the resin composition is not particularly limited, and known materials can be used.
- Specific examples of radical polymerization initiators include dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis(2-t-butylperoxyisopropyl)benzene, or 2,5-dimethyl-2,5-bis( Dialkyl peroxides such as t-butylperoxy)hexane; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1- bis(t-amylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, or ethyl 3,3-(t-butylperoxy) Peroxyketals such as butyrate;
- Examples include 1-hydroxycyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2 -methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone , 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated
- the content of the radical polymerization initiator of component (B) is not particularly limited.
- the component (B) radical polymerization initiator is preferably 0.01 to 40% by mass, more preferably 0.03 to 30% by mass, and still more preferably 0.05 to 20% by mass in the resin composition. It is preferable that
- ((C) component) Component (C) is at least one of (C1) a polyfunctional thiol compound and (C2) an acrylate compound.
- the resin composition preferably contains at least one of (C1) a polyfunctional thiol compound and (C2) an acrylate compound in addition to the components (A) and (B) described above.
- ((C1) component) (C1) A component is a polyfunctional thiol compound.
- the (C1) component polyfunctional thiol compound imparts elasticity to the resin composition.
- Component (C1) is not particularly limited as long as it has two or more functional groups. However, from the viewpoint of moisture resistance, the component (C1) is preferably a non-hydrolyzable thiol that does not contain an ester bond in its molecule because it suppresses hydrolysis during moisture resistance.
- (C1) polyfunctional thiol compound preferably has a molecular weight of 500 or less and is liquid at room temperature.
- the (C1) component includes a glycoluril compound represented by the following general formula (1).
- R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.
- n is an integer from 0 to 10;
- the (C1) component may be a compound represented by the following chemical formula (2) or chemical formula (3).
- the compound represented by chemical formula (2) or chemical formula (3) is more preferable as the component (C1).
- polyfunctional thiol resins having no ester bond in the molecule include polyfunctional thiol resins represented by general formula (4).
- R 3 , R 4 , R 5 and R 6 are each independently hydrogen or C n H 2n SH (n is 2 to 6). Further, at least one of R 3 , R 4 , R 5 and R 6 is C n H 2n SH (n is 2-6). 2 to 4 of R 3 , R 4 , R 5 and R 6 are preferably C n H 2n SH (n is 2 to 6), and 3 of R 3 , R 4 , R 5 and R 6 More preferably, one or four are C n H 2n SH (n is 2-6). Further, n of the polyfunctional thiol compound (C1) component represented by the general formula (4) is preferably 2 to 4 from the viewpoint of curability.
- the thiol compound is more preferably a mercaptopropyl group in which n is 3 from the viewpoint of the balance between the physical properties of the cured product and the curing speed.
- the (C1) component represented by the general formula (4) has a sufficiently flexible skeleton itself, and is effective when it is desired to lower the elastic modulus of the cured product. By adding the component (C1) represented by the general formula (4), the elastic modulus of the cured product can be controlled, so that the adhesive strength (especially peel strength) after curing can be increased.
- component (C1) Commercially available products of component (C1) include Shikoku Kasei Co., Ltd. thiol glycol uril derivative (product name: TS-G (corresponding to chemical formula (2), thiol equivalent: 100 g / eq), C3TS-G (corresponding to chemical formula (3) equivalent, thiol equivalent: 114 g/eq)), and a thiol compound manufactured by SC Organic Chemical Co., Ltd. (product name: Multithiol Y-3 (in general formula (4), the main component corresponds to trifunctional thiol)).
- a single component may be used, or two or more components may be used in combination.
- the component (C1) contains 50 to 100 parts by mass of a glycoluril compound with respect to 100 parts by mass of the component (C1) from the viewpoint of maintaining the shear strength after curing of the resin composition.
- the content of the glycoluril compound in component (C1) is more preferably 60 to 100 parts by mass, even more preferably 70 to 100 parts by mass.
- a polyfunctional thiol resin having an ester bond in the molecule can also be used as the (C1) component.
- the content of the polyfunctional thiol resin is preferably 50 to 100 parts by mass per 100 parts by mass of the component (C1) from the viewpoint that the ester bond can impart flexibility to the cured product.
- the content of the polyfunctional thiol resin having an ester bond in the molecule is 50 parts by mass with respect to 100 parts by mass of the component (C1). part, more preferably less than 40 parts by mass, and even more preferably less than 30 parts by mass.
- Polyfunctional thiol resins having an ester bond in the molecule include, for example, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercapto propionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis( 3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, tri Methylolpropane tris (3-mercaptobutyrate), tri
- the (C2) component is an acrylate compound.
- the resin composition may further contain an acrylate compound as component (C2) in addition to the methacrylate compound as component (A).
- the acrylate compound is preferably a polyfunctional acrylate compound having two or more acryloyl groups.
- the polyfunctional acrylate compound is more preferably bifunctional from the viewpoint of jet dispensing properties. If it is trifunctional or more, the jet dispensing property may become disadvantageous.
- the acrylate compound (C2) preferably has a functional group equivalent weight of 100 or more and 500 or less, more preferably 100 or more and 400 or less, and 100 or more and 250 or less. It is even more preferable to have The number of functional groups is preferably 1-6, more preferably 1-4, and even more preferably 2 or 3.
- (C2) preferably contains a benzene ring in the molecule in order to make the physical properties of the cured resin composition highly heat-resistant and highly reliable.
- the resin composition does not contain a benzene ring in order to make the physical properties of the resin composition after curing low in elasticity.
- acrylate compound examples include N-acryloyloxyethylhexahydrophthalimide, acryloylmorpholine, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexane-1,4-dimethanol monoacrylate, tetrahydrofuro furyl acrylate, phenoxyethyl acrylate, phenyl polyethoxy acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, o-phenylphenol monoethoxy acrylate, o-phenylphenol polyethoxy acrylate, p-cumylphenoxyethyl acrylate, isobornyl acrylate , tribromophenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 1,4-butanediol diacrylate, 1,6-hex
- the resin composition contains both (C1) a polyfunctional thiol compound and (C2) an acrylate compound as the (C) component
- the ratio of the total number of (meth)acryloyl groups of (A) methacrylate compound and (C2) acrylate compound to the total number of thiol groups of (C1) polyfunctional thiol compound is 0.8 to 1.2. preferable.
- the reactivity of the resin composition can be improved by setting the ratio of the total number of functional groups of each component as described above.
- the total number of (meth)acryloyl groups for (A) the methacrylate compound and (C2) the acrylate compound is the total number of methacryloyl groups for (A) the methacrylate compound and the total number of acryloyl groups for (C2) the acrylate compound.
- the number of methacryloyl groups of the (A) methacrylate compound relative to the total number of thiol groups of the (C1) polyfunctional thiol compound Preferably the ratio is between 0.8 and 1.2.
- the numerical range as above, extremely excellent jet dispensing properties can be realized.
- (A) the total number of methacryloyl groups for methacrylate compounds, (C2) the total number of acryloyl groups for acrylate compounds, and (C1) the total number of thiol groups for polyfunctional thiol compounds will be described.
- methacryloyl groups are counted as the total number of methacryloyl groups for (A) methacrylate compounds, and acryloyl groups are counted as the total number of acryloyl groups for (C2) acrylate compounds.
- a silane coupling agent having a thiol group or (meth)acryloyl group is not counted in the total number of components (A), (C2) and (C1).
- (A) the total number of methacryloyl groups for the methacrylate compound, (C2) the total number of acryloyl groups for the acrylate compound, and (C1) the total number of thiol groups for the polyfunctional thiol compound can be determined by, for example, NMR, gas chromatography, It can be determined by an analysis method such as liquid phase chromatography.
- ((D) component) (D) Component is an anionic polymerization initiator.
- the resin composition may further contain an anionic polymerization initiator as component (D) in addition to the radical polymerization initiator as component (B).
- Such an anionic polymerization initiator is a polymerization initiator that initiates polymerization when heated. For example, when the resin composition is used as an adhesive for electronic parts, it is effectively used during main curing after temporary fixing. .
- anionic polymerization initiator that can be used in the resin composition is not particularly limited, and known materials can be used. Specific examples of anionic polymerization initiators include imidazole compounds that are solid at room temperature, solid-dispersed amine adduct-based latent curing accelerators such as reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems), A reaction product (urea-type adduct system) of an amine compound and an isocyanate compound or a urea compound is included.
- imidazole compounds that are solid at room temperature examples include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl- 5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-S-triazine, 2,4-diamino -6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl -2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-pheny
- Examples of the epoxy compound used as one of raw materials for producing the solid-dispersed amine adduct-based latent curing accelerator (amine-epoxy adduct-based) that can be used in the present invention include bisphenol A, bisphenol F, catechol, and resorcinol.
- Polyglycidyl ether obtained by reacting polyhydric phenol such as polyhydric phenol, or polyhydric alcohol such as glycerin or polyethylene glycol with epichlorohydrin; p-hydroxybenzoic acid, hydroxycarboxylic acid such as ⁇ -hydroxynaphthoic acid glycidyl ether esters obtained by reacting with epichlorohydrin; polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; 4,4'-diaminodiphenylmethane and glycidylamine compounds obtained by reacting m-aminophenol or the like with epichlorohydrin; further polyfunctional epoxy compounds such as epoxidized phenol novolak resins, epoxidized cresol novolak resins, and epoxidized polyolefins; butyl glycidyl ether; monofunctional epoxy compounds such as phen
- the amine compound used as another raw material for producing the solid-dispersed amine adduct-based latent curing accelerator has one or more active hydrogens in the molecule capable of undergoing an addition reaction with an epoxy group, and a primary amino group, Any compound having at least one functional group selected from a secondary amino group and a tertiary amino group in the molecule may be used. Examples of such amine compounds are shown below, but are not limited thereto.
- aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexylmethane; 4,4'-diaminodiphenylmethane; , aromatic amine compounds such as 2-methylaniline; nitrogen atom-containing heterocycles such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, piperazine compounds; and the like.
- compounds having a tertiary amino group in the molecule in particular are raw materials that provide latent curing accelerators having excellent curing accelerating ability.
- examples of such compounds include, for example, dimethylaminopropyl Amine compounds such as amine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, 2-methylimidazole, 2-ethylimidazole, 2-ethyl - Primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as 4-methylimidazole and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol , 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethyl
- Examples of the isocyanate compound used as another production raw material for the solid-dispersed amine adduct latent curing accelerator include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate.
- terminal isocyanate group-containing compounds examples include an addition compound having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and trimethylolpropane, and a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and pentaerythritol. but not limited thereto.
- urea compounds include urea and thiourea, but are not limited to these.
- the solid dispersion type latent curing accelerator that can be used in the present invention can be obtained, for example, by the following method. First, the two components of (a) the amine compound and the epoxy compound, (b) the three components of the two components and the active hydrogen compound, or (c) at least one of the amine compound and the isocyanate compound and the urea compound. Each component is taken and mixed in a combination of two or three components. The resulting mixture is then reacted at a temperature between room temperature and 200°C.
- the obtained reactant is solidified by cooling and pulverized, or reacted in a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc., and after removal of the solvent, the solid content is pulverized to obtain the above-mentioned solid dispersion type latent.
- a hardening accelerator can be easily obtained.
- the amine-epoxy adduct system includes "Amicure PN-23" (manufactured by Ajinomoto Co., Ltd., trade name), "Amicure PN-40” (manufactured by Ajinomoto Co., Ltd., trade name), "Amicure PN -50" (manufactured by Ajinomoto Co., Ltd., trade name), "Hardner X-3661S” (manufactured by ACR, trade name), “Hardner X-3670S” (manufactured by ACR, trade name), "Novacure HX-3742” (manufactured by Asahi Kasei, trade name), “Novacure HX-3721” (manufactured by Asahi Kasei, trade name), "Novacure HX
- the content of the anionic polymerization initiator of component (D) is not particularly limited.
- the anionic polymerization initiator of component (D) is included, it is preferably contained in the resin composition at a ratio of 0.5 to 10% by mass, preferably 1 to 5% by mass. More preferably, 1 to 3% by mass is even more preferable.
- ((E) component) (E) Component is a polymerization inhibitor.
- the (E) component polymerization inhibitor is added to enhance the stability of the resin composition during storage.
- polymerization inhibitors include radical polymerization inhibitors.
- the component (E), a radical polymerization inhibitor is added to suppress the progress of unintended radical polymerization reactions.
- the methacrylate compound (A) component and the acrylate compound (C2) component may generate radicals by themselves with a low probability. At this time, an unintended radical polymerization reaction may proceed from the radical as a starting point.
- a radical polymerization inhibitor it is possible to suppress the progress of such unintended radical polymerization reactions of the components (A) and (C2).
- a known polymerization inhibitor can be used as the component (E).
- Component (E) used is preferably at least one selected from the group consisting of, for example, N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone.
- known radical polymerization inhibitors disclosed in JP-A-2010-117545 and JP-A-2008-184514 can also be used as the component (E).
- a single component may be used, or two or more components may be used in combination.
- a component is a filler.
- a filler By including a filler as the component (F), it is possible to improve the moisture resistance and the ability to drain liquid during jet dispensing.
- the content of the filler is not particularly limited. It is more preferable to contain up to 30% by mass.
- a known filler can be used as the component (F).
- an inorganic filler and an organic filler are mentioned, for example.
- inorganic fillers include glass, silica, alumina, aluminum nitride, boron nitride, titanium oxide, calcium carbonate, talc, and silver fillers.
- organic fillers include silicone rubber, PTFE, polystyrene, polyacrylate, polyurethane, and polydivinylbenzene fillers.
- the average particle size of the filler is preferably 0.1 to 10 ⁇ m, more preferably 0.3 to 5 ⁇ m, even more preferably 0.5 to 5 ⁇ m.
- ((G) component) (G) Component is a black pigment.
- the black pigment as component (G) is a particularly effective component when the resin composition is used as an adhesive that requires light shielding properties, such as an adhesive for camera modules.
- an adhesive for camera modules For example, when a resin composition is used as an adhesive for a camera module, light may enter the camera module from a portion coated with the resin composition. For this reason, it is preferable to contain a black pigment as the component (G) in order to prevent light from entering the camera module and provide light shielding properties.
- a known black pigment can be used as the component (G).
- Examples of the (G) component used include carbon black, graphite, titanium nitride, titanium oxide, zirconia, and titanium black.
- the resin composition may contain (H) an anionic polymerization inhibitor (hereinafter also referred to as "(H) component”) within a range that does not impair the effects of the present invention.
- (H) The anionic polymerization inhibitor is for enhancing the stability of the resin composition during storage, and is added to suppress the occurrence of polymerization reaction due to unintended basic components.
- (H) A known anionic polymerization inhibitor can be used, for example, a boric acid ester compound and a strong acid can be used.
- Specific examples of (H) anionic polymerization inhibitors include trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, trifluoromethanesulfonic acid, maleic acid, methanesulfonic acid, barbituric acid, and difluoroacetic acid. , trichloroacetic acid, phosphoric acid, and dichloroacetic acid.
- the preferred (H) anionic polymerization inhibitor is at least one selected from tri-n-propylborate, triisopropylborate and barbituric acid.
- anionic polymerization inhibitor known ones disclosed in JP-A-2010-117545, JP-A-2008-184514, JP-A-2017-171804, etc. can also be used.
- the anionic polymerization inhibitor may be used alone or in combination of two or more.
- the content of component (H) is preferably 0.1 to 10% by mass, more preferably 0.3 to 7% by mass, relative to the total mass of the resin composition.
- the resin composition used in the ejection method of the present embodiment may further contain components other than components (A) to (H) described above, if necessary.
- Specific examples of such components include antifoaming agents, silane coupling agents, dispersants, and epoxy resins.
- the type and amount of each compounding agent are as per usual methods.
- the resin composition used in the ejection method of this embodiment preferably has, for example, the following properties.
- the viscosity of the resin composition is preferably 0.2 to 80 Pa ⁇ s, more preferably 1 to 60 Pa ⁇ s, even more preferably 1 to 50 Pa ⁇ s. With such a configuration, the resin composition can be easily handled and maintain high fluidity.
- the viscosity of the resin composition can be measured using a Brookfield (B-type) viscometer using an SC4-14 spindle at room temperature (25° C.) and a rotational speed of 50 rpm.
- the TI (thixotropy index) of the resin composition is preferably 0.7 to 7, more preferably 0.9 to 6.5, and 1 to 6.5 at room temperature (25°C). is more preferred.
- the thixotropy index of the resin composition is, for example, measured using a SC4-14 spindle at room temperature (25° C.) at a rotational speed of 5 rpm using a Brookfield (B type) viscometer. It can be measured by dividing by the value measured by the rotational speed.
- the resin composition used in the ejection method of this embodiment can be produced by a conventional method.
- the resin composition can be produced by mixing each component described above using, for example, a Laikai machine, a pot mill, a three-roll mill, a rotary mixer, a twin-screw mixer, or the like.
- the configuration of the jet dispenser used in the ejection method of the present embodiment is not particularly limited as long as the material of the member that collides with the nozzle is made of metal. can be configured.
- the conditions for discharging the resin composition by the jet dispenser are not particularly limited, and as long as the resin composition described above is discharged, the discharge conditions for conventionally known jet dispensers should be followed. can be done.
- the jet dispenser used in the ejection method of this embodiment is preferably configured as follows. Metal nozzles are preferred.
- the nozzle temperature may be room temperature or may be heated.
- the tip diameter of the needle is preferably 0.7 to 3 mm.
- the needle pull-up time is preferably 0.1 to 7 msec, and the needle pull-down time is preferably 0.1 to 7 msec.
- the needle lifting distance is preferably 0.1 to 1 mm.
- the inner diameter of the nozzle is preferably 50-200 ⁇ m.
- the syringe pressure is preferably 0.01-0.5 MPa.
- the discharge method of this embodiment can be used in the step of applying an adhesive for electronic components.
- the resin composition is used as an adhesive for electronic parts.
- the resin composition can be suitably applied to engineering plastics.
- the electronic parts to be adhered are not particularly limited, and examples thereof include ceramic substrates, organic substrates, and semiconductor chips.
- the resin composition is used in the step of applying an adhesive for electronic parts with a jet dispenser 50 as shown in FIG.
- the resin composition can be effectively used, for example, as an adhesive for camera modules. That is, it can be used for bonding members constituting a camera module to each other, and can be mainly used for fixing members to each other using UV. As for the fixation of the members, it can be used for temporary fixation in the active alignment process and permanent fixation for finally fixing the camera module.
- the resin composition used in the ejection method of the present embodiment can meet the requirement of fluidity required when fixing the camera module.
- the jet dispenser 50 as shown in FIG. 1 can jet several hundred shots per second by reciprocating the needle 52 . Therefore, a large impact is applied to the resin composition 20 (for example, adhesive) for jet dispensing. Even after being subjected to such a large impact, the resin composition 20 can maintain fluidity.
- the resin composition 20 for example, adhesive
- a jet dispenser is used to supply the adhesive for fixing the components of the camera module.
- the width of the minute area or gap to which the adhesive is supplied is several hundred ⁇ m (for example, 300 ⁇ m). If the resin composition is jet-dispensed, the adhesive can be delivered to areas and crevices of small dimensions.
- the method for manufacturing an electronic component according to this embodiment is a method for manufacturing an electronic component using the discharge method according to this embodiment described above.
- the method of manufacturing an electronic component according to the present embodiment can accurately apply a very small amount of adhesive for electronic components to a very small area by using the discharge method described above. Therefore, the method for manufacturing an electronic component according to the present embodiment is a very effective manufacturing method for manufacturing a small electronic component that requires bonding.
- the electronic component of the present embodiment is an electronic component obtained by the method for manufacturing an electronic component described above.
- good adhesion between electronic members is achieved. Therefore, the productivity is high and the reliability is high.
- Examples 1-23, Comparative Examples 1-2 [Preparation of resin composition] After weighing and blending each component shown in Tables 1 to 4, they were mixed to prepare a resin composition used in the ejection method of Examples and Comparative Examples. Specifically, each component shown in Tables 1 to 4 was mixed with a planetary mixer, dispersed with a three-roll mill, and pasted to prepare a resin composition. Details of each component shown in Tables 1 to 4 are as follows.
- (A) component; methacrylate compound] (A-1): Phenoxyethyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (trade name: Light Ester PO, methacrylate equivalent: 206 g/eq, number of methacryloyl groups per molecule: 1).
- (A-2) Bisphenol A/EO 2.6 mol adduct-dimethacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (trade name: Light Ester BP-2EMK, methacrylate equivalent: 181 g/eq, number of methacryloyl groups in one molecule: 2 Individual).
- A-3) Neopentyl glycol dimethacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (trade name: Light Ester NP, methacrylate equivalent: 120 g/eq, number of methacryloyl groups per molecule: 2).
- A-4) Trimethylolpropane trimethacrylate, manufactured by Shin-Nakamura Chemical (trade name: NK Ester TMPT, methacrylate equivalent: 112.8 g/eq, number of methacryloyl groups per molecule: 3).
- A-5) Ditrimethylolpropane tetramethacrylate, manufactured by Shin-Nakamura Chemical (trade name: NK Ester D-TMP, methacrylate equivalent: 129.5 g/eq, number of methacryloyl groups per molecule: 4).
- A-6 2-hydroxy-1,3-dimethacryloxypropane, manufactured by Shin-Nakamura Chemical (trade name: NK Ester 701, methacrylate equivalent: 114 g/eq, number of methacryloyl groups per molecule: 2) .
- (B) component; radical polymerization initiator (B-1): 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, manufactured by NOF Corporation (trade name: Perocta O, thermal radical polymerization initiator).
- B-2) 1-hydroxycyclohexyl-phenyl ketone, IGM ResinsB. V. (trade name: OMNIRAD 184, photoradical polymerization initiator).
- (C) component [(C1) component]; polyfunctional thiol compound] (C1-1): Tetrahydro-1,3,4,6-tetrakis(3-mercaptopropyl)-imidazo[4,5-d]imidazole-2,5(1H,3H)-dione, manufactured by Shikoku Kasei Co., Ltd. (trade name: C3TS-G, thiol equivalent: 110 g/eq, number of thiol groups in one molecule: 4).
- (C) component [(C2) component]; acrylate compound] (C2-1): Polyester acrylate (polyfunctional acrylic compound) manufactured by Toagosei Co., Ltd. (trade name: M7100, acrylate equivalent: 188 g/eq, number of acryloyl groups per molecule: 3 or more).
- (D) component; anionic polymerization initiator [(D) component; anionic polymerization initiator]
- D-1) A mixture of a microencapsulated amine-based curing agent and bisphenol A-type and F-type epoxy resins, in which 33% by mass of the amine-based curing agent is microencapsulated, manufactured by Asahi Kasei Corporation (trade name: HXA9322 HP).
- D-2) Modified alicyclic polyamine, manufactured by T&K TOKA (trade name: FXR-1121).
- E-1 N-nitroso-N-phenylhydroxylamine aluminum, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. (trade name: Q-1301).
- E-2) 4-tert-butylpyrocatechol, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. (trade name: t-butylcatechol).
- F-1 Spherical silica, manufactured by Admatechs (trade name: SE5200 SEE).
- F-2) Spherical silica, manufactured by Admatechs (trade name: SE2200 SEE).
- F-3) Silicone composite powder, manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: KMP 600T).
- F-4) Fumed silica, manufactured by Cabot Corporation (trade name: TS-720).
- G-1 Carbon black, manufactured by Evonik Degussa Japan (trade name: Black 4).
- G-2) Titanium nitride, titanium dioxide, manufactured by Mitsubishi Materials Electronic Chemicals (trade name: Titanium Black 13M).
- (I) component; other components (I-1): Silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: KBM403; 3-glycidoxypropyltrimethoxysilane).
- the functional group ratio (1) is the ratio of the total number of methacryloyl groups of component (A) to the total number of acryloyl groups of component (C2) (that is, the total number of methacryloyl groups of component (A)/(C2) total number of acryloyl groups in the component).
- the functional group ratio (2) is the ratio of the total number of methacryloyl groups of component (A) and the total number of acryloyl groups of component (C2) to the total number of thiol groups of component (C1) (i.e. ⁇ component (A) total number of methacryloyl groups + total number of acryloyl groups in component (C2) ⁇ /total number of thiol groups in component (C1)).
- the results of functional group ratio (1) and ratio (2) for each component are shown in Tables 1-4.
- Example 23 and Comparative Example 2 the jet dispensing performance was evaluated using Vermes' trade name "MDS3200A".
- a metal member made of tungsten carbide was used for the needle, which is a member that collides with the nozzle when the resin composition is discharged.
- a jet dispenser was used in which the material of the needle, which collides with the nozzle when the resin composition is discharged, is made of ceramic.
- the resin compositions of Examples 1 to 23 and Comparative Examples 1 and 2 which were continuously discharged by a jet dispenser as described above, were evaluated for curability and jet dispensability by the following methods. The results are shown in Tables 1-4.
- the resin composition discharged by the jet dispenser was subjected to UV curing or heat curing, and the UV curing depth or the strength at the time of heat curing was measured.
- ⁇ UV curing depth> Two heat-resistant tapes (thickness: 100 ⁇ m) were pasted on a black resin plate A (width: 50 mm ⁇ length: 25 mm ⁇ thickness: 1.5 mm) at intervals of 10 mm. Next, the resin composition was applied between the two heat-resistant tapes on the resin plate A so as to have the same thickness of 100 ⁇ m as the heat-resistant tape.
- the integrated amount of light was measured by connecting a receiver "UVD-365 (trade name)" of "UIT-250 (trade name)” manufactured by Ushio Inc.. Peel off one of the sandwiched resin plates A and B, remove the uncured portion attached to the cured product of the resin composition, measure the distance of the cured portion from the UV irradiation surface with a microscope, and measure the UV curing depth. and ⁇ Strength at thermosetting> A 2 mm ⁇ 3 mm ceramic chip was placed on each of the resin compositions of Examples and Comparative Examples that were jet-dispensed onto a ceramic substrate.
- UV curing was performed by UV irradiation with an integrated light amount of 2000 mJ/cm 2 using a UV LED irradiation device “AC475 (trade name)” manufactured by Excelitas Technologies.
- the integrated amount of light was measured by connecting a receiver "UVD-365 (trade name)” of "UIT-250 (trade name)” manufactured by Ushio Inc..
- the UV-cured curable resin composition was thermally cured at 80° C. for 60 minutes in a blower dryer.
- DAGE4000 universal bond tester
- the cured product cured as described above was evaluated according to the following evaluation criteria. In the following evaluation criteria, the evaluation of "A" is the best, and the evaluation is inferior in the order of " ⁇ " and " ⁇ ".
- the UV curing depth is more than 350 ⁇ m and less than 450 ⁇ m, or the strength at the time of heat curing is more than 60 N and less than 130 N.
- A The number of shots that can be discharged continuously is 100,000 times or more.
- Good The number of shots that can be ejected continuously is 10,000 or more and less than 100,000.
- ⁇ The number of shots that can be ejected continuously is 500 or more and less than 10,000.
- x The number of shots that can be continuously ejected is less than 500, or the sliding portion 61 or the collision portion 62 as shown in FIG. When a gelled product is generated at the collision part 62) that collides with.
- the material of the member that collides with the nozzle during ejection of the resin composition is made of ceramic. It is presumed that the heat generated in the jet dispenser was hard to escape to the outside, and the resin composition was partially cured inside the jet dispenser.
- the method for discharging a resin composition of the present invention can be used for applying a resin composition by jet dispensing, and in particular, it can be effectively used as a method for applying an adhesive, for example, an adhesive for electronic parts. can. Therefore, the method for discharging the resin composition of the present invention can be suitably used for manufacturing electronic parts, for example.
- the method for manufacturing an electronic component and the electronic component of the present invention can be used for a method for manufacturing an electronic component having a bonding step using an adhesive for electronic components and for an electronic component manufactured by this manufacturing method.
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Abstract
Description
前記ジェットディスペンサーとして、前記樹脂組成物の吐出時に前記ノズルと衝突する部材の材質が金属製のものを用い、且つ、
前記樹脂組成物が、(A)メタクリレート化合物及び(B)ラジカル重合開始剤を含む、樹脂組成物の吐出方法。
本発明の樹脂組成物の吐出方法の一の実施形態は、図1に示すような、ジェットディスペンサー50を用い、当該ジェットディスペンサー50のノズル56から樹脂組成物20を吐出する樹脂組成物の吐出方法である。ここで、図1は、ジェットディスペンス装置(ジェットディスペンサー50)の一例の断面模式図である。ジェットディスペンサー50は、ピストンのように往復運動が可能なニードル52と、ニードル52の往復運動によっても外部に樹脂組成物20が漏れないようにするためのシール54(密封部材)と、樹脂組成物20をジェットディスペンスするためのノズル56とを有する。
(A)成分は、メタクリレート化合物である。(A)成分は、メタクリロイル基を有していれば特に制限はない。例えば、(A)成分のメタクリレート化合物における官能基数(即ち、メタクリロイル基の数)については特に制限はない。(A)メタクリレート化合物を含むものとすることで、樹脂組成物の反応性を制御することができ、ジェットディスペンサー内部での樹脂組成物のゲル化を起こり難くすることができる。
(B)成分は、ラジカル重合開始剤である。樹脂組成物は、(B)成分としてラジカル重合開始剤を含むものであるため、短時間の加熱やUV照射で、樹脂組成物を硬化させることが可能となる。(B)成分のラジカル重合開始剤は、熱ラジカル重合開始剤単独でもよいし、光ラジカル重合開始剤単独でもよいし、これらの2種を併用してもよい。(B)成分のラジカル重合開始剤は、より好ましくは光ラジカル重合開始剤である。
(C)成分は、(C1)多官能チオール化合物及び(C2)アクリレート化合物のうちの少なくとも一方である。このように、樹脂組成物は、上述した(A)成分及び(B)成分に加えて、(C1)多官能チオール化合物及び(C2)アクリレート化合物のうちの少なくとも一方を含むものであることが好ましい。
(C1)成分は、多官能チオール化合物である。(C1)成分の多官能チオール化合物は、樹脂組成物に、弾性を付与する。(C1)成分は、2以上の官能基を有していれば、特に限定されない。ただし、耐湿性の観点から、(C1)成分は、耐湿時の加水分解を抑制するため、分子内にエステル結合を含まない非加水分解性チオールが好ましい。
(C2)成分は、アクリレート化合物である。樹脂組成物は、(A)成分のメタクリレート化合物に加えて、更に、(C2)成分としてのアクリレート化合物を含んでいてもよい。
(D)成分は、アニオン重合開始剤である。樹脂組成物は、(B)成分としてのラジカル重合開始剤に加えて、(D)成分として更にアニオン重合開始剤を含んでいてもよい。このようなアニオン重合開始剤は、加熱時に重合を開始させる重合開始剤であり、例えば、樹脂組成物を電子部品用接着剤として用いた際に、仮固定後の本硬化時に有効に使用される。
(E)成分は、重合禁止剤である。(E)成分の重合禁止剤は、樹脂組成物の保存時の安定性を高めるために添加される。例えば、重合禁止剤として、ラジカル重合禁止剤が挙げられる。(E)成分のラジカル重合禁止剤は、意図しないラジカル重合反応の進行を抑制するために添加される。(A)成分のメタクリレート化合物や(C2)成分のアクリレート化合物は、低い確率で、自分からラジカルを発生することがある。このとき、そのラジカルを基点として、意図しないラジカル重合反応が進行する場合がある。ラジカル重合禁止剤を添加することによって、このような意図しない(A)成分や(C2)成分のラジカル重合反応の進行を抑制することができる。
(F)成分は、フィラーである。(F)成分としてのフィラーを含むことにより、耐湿性とジェットディスペンス時の液切れ性の向上を図ることができる。フィラーの含有量については特に制限はないが、例えば、樹脂組成物中に、(F)成分のフィラーを0~65質量%含むことが好ましいく、5~50質量%含むことがより好ましく、10~30質量%含むことがさらに好ましい。
(G)成分は、黒色顔料である。(G)成分としての黒色顔料は、樹脂組成物を、カメラモジュール用接着剤などの遮光性が求められる接着剤として使用する際に特に有効な成分である。例えば、カメラモジュール用接着剤として樹脂組成物を使用した場合、樹脂組成物を塗布した部位からカメラモジュール内に光が入ることがある。このため、光がカメラモジュール内に入ることを防ぐため遮光性をもたすために、(G)成分として黒色顔料を含むことが好ましい。
樹脂組成物は、本発明の効果を損なわない範囲で、(H)アニオン重合抑制剤(以下、「(H)成分」とも言う)を含んでもよい。(H)アニオン重合抑制剤は、樹脂組成物の保存時の安定性を高めるためのものであり、意図しない塩基性成分による重合反応の発生を抑制するために添加される。
本実施形態の吐出方法に用いられる樹脂組成物は、これまでに説明した(A)成分~(H)成分以外の成分を必要に応じて更に含有してもよい。このような成分の具体例としては、消泡剤、シランカップリング剤、分散剤、エポキシ樹脂などを配合することができる。各配合剤の種類、配合量は常法通りである。
本実施形態の吐出方法に用いられる樹脂組成物は、例えば、以下に示す特性を有していることが好ましい。樹脂組成物の粘度が、0.2~80Pa・sであることが好ましく、1~60Pa・sであることがより好ましく、1~50Pa・sであることが更に好ましい。このように構成することによって、樹脂組成物の取扱い性が良好であり、流動性を高く保つことができる。樹脂組成物の粘度は、ブルックフィールド社製(B型)粘度計を用いて、SC4-14スピンドルを用いて、室温(25℃)で、50rpmの回転速度で測定することができる。
本実施形態の吐出方法に用いられる樹脂組成物は、慣用の方法により製造することができる。樹脂組成物は、これまでに説明した各成分を、例えば、ライカイ機、ポットミル、三本ロールミル、回転式混合機、二軸ミキサー等を用いて混合することで製造することができる。
本実施形態の吐出方法に使用されるジェットディスペンサーの構成については、ノズルと衝突する部材の材質が金属製であれば、その他の構成に関しては特に制限はなく、従来公知のジェットディスペンサーに準じた装置構成とすることができる。また、ジェットディスペンサーにより樹脂組成物を吐出する際の条件についても特に制限はなく、これまでに説明した樹脂組成物を吐出する限りにおいて、従来公知のジェットディスペンサーの吐出条件に準じたものとすることができる。例えば、本実施形態の吐出方法に使用されるジェットディスペンサーは、以下のように構成されたものであることが好ましい。金属製のノズルが好ましい。ノズル温度は、常温でも良いし加温しても良い。ニードルの先端径は、0.7~3mmが好ましい。ニードルの引き上げ時間は、0.1~7msecが好ましく、ニードルの引き下げ時間は、0.1~7msecが好ましい。ニードル引き上げ距離は、0.1~1mmが好ましい。ノズル内径は、50~200μmが好ましい。シリンジ圧は、0.01~0.5MPaが好ましい。
本実施形態の吐出方法は、電子部品用接着剤を塗布する工程に用いることができる。このような工程において、樹脂組成物は、電子部品用接着剤として用いられる。また、樹脂組成物は、エンジニアプラスチックに対しても好適に適応することができる。本実施形態の吐出方法において、樹脂組成物を電子部品用接着剤として用いた場合に、接着対象となる電子部品については特に制限はなく、セラミック基板や有機基板、半導体チップ等が挙げられる。特に、接着剤として用いる場合には、小型の電子部品の接着に有用である。樹脂組成物は、図1に示すようなジェットディスペンサー50によって電子部品用接着剤を塗布する工程に利用される。
次に、本発明の電子部品の製造方法の実施形態について説明する。本実施形態の電子部品の製造方法は、これまでに説明した本実施形態の吐出方法を用いた電子部品の製造方法である。特に、本実施形態の電子部品の製造方法は、これまでに説明した吐出方法を用いることで、微小量の電子部品用の接着剤を微小領域に的確に塗布することができる。このため、本実施形態の電子部品の製造方法は、小型の電子部品の接着を要する製造方法として極めて有効な製造方法である。
次に、本発明の電子部品の実施形態について説明する。本実施形態の電子部品は、上述した電子部品の製造方法によって得られた電子部品である。本実施形態の電子部品は、電子部材同士の良好な接着が実現されている。このため、生産性が高く、また、信頼性の高いものである。
〔樹脂組成物の作製〕
表1~表4に示す各成分を計量配合した後、それらを混合して、実施例及び比較例の吐出方法に用いる樹脂組成物を調製した。具体的には、表1~表4に示す各成分を、プラネタリーミキサーで混合し、更に三本ロールミルで分散し、ペースト化することによって樹脂組成物を調製した。表1~表4に示す各成分の詳細については以下の通りである。
(A-1):フェノキシエチルメタクリレート、共栄社化学社製(商品名:ライトエステルPO、メタクリレート当量:206g/eq、1分子中のメタクリロイル基の数:1個)。
(A-2):ビスフェノールA・EO2.6モル付加物-ジメタクリレート、共栄社化学社製(商品名:ライトエステルBP-2EMK、メタクリレート当量:181g/eq、1分子中のメタクリロイル基の数:2個)。
(A-3):ネオペンチルグリコールジメタクリレート、共栄社化学社製(商品名:ライトエステルNP、メタクリレート当量:120g/eq、1分子中のメタクリロイル基の数:2個)。
(A-4):トリメチロールプロパントリメタクリレート、新中村化学製(商品名:NKエステルTMPT、メタクリレート当量:112.8g/eq、1分子中のメタクリロイル基の数:3個)。
(A-5):ジトリメチロールプロパンテトラメタクリレート、新中村化学製(商品名:NKエステルD-TMP、メタクリレート当量:129.5g/eq、1分子中のメタクリロイル基の数:4個)。
(A-6):2-ヒドロキシ-1,3-ジメタクリロキシプロパン、新中村化学製(商品名:NKエステル701、メタクリレート当量:114g/eq、1分子中のメタクリロイル基の数:2個)。
(B-1):1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート、日本油脂社製(商品名:パーオクタO、熱ラジカル重合開始剤)。
(B-2):1-ヒドロキシシクロヘキシル-フェニルケトン、IGM ResinsB.V.社製(商品名:OMNIRAD 184、光ラジカル重合開始剤)。
(B-3):2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパン-1-オン、IGM ResinsB.V.社製(商品名:OMNIRAD 907、光ラジカル重合開始剤)。
(C1-1):テトラヒドロ-1,3,4,6-テトラキス(3-メルカプトプロピル)-イミダゾ[4,5-d]イミダゾール-2,5(1H,3H)-ジオン、四国化成工業社製(商品名:C3TS-G、チオール当量:110g/eq、1分子中のチオール基の数:4個)。
(C1-2):ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)、SC有機化学社製(商品名:PEMP-LV、チオール当量:122g/eq、1分子中のチオール基の数:4個)。
(C1-3):3-(3-メルカプト-プロポキシ)-2,2-ビス-(3-メルカプト-プロポキシメチル)-プロパン-1-オール、SC有機化学社製(商品名:Multhiol Y-3、チオール当量:124g/eq、1分子中のチオール基の数:3個)。
(C2-1):ポリエステルアクリレート(多官能アクリル化合物)、東亜合成社製(商品名:M7100、アクリレート当量:188g/eq、1分子中のアクリロイル基の数:3個以上)。
(C2-2):ジメチロール-トリシクロデカンジアクリレート、共栄社化学社製(商品名:ライトアクリレートDCP-A、アクリレート当量:152g/eq、1分子中のアクリロイル基の数:2個)。
(C2-3):ネオペンチルグリコールジアクリレート、共栄社化学社製(商品名:ライトアクリレートNP-A、アクリレート当量:106g/eq、1分子中のアクリロイル基の数:2個)。
(D-1):マイクロカプセル化されたアミン系硬化剤とビスフェノールA型、F型エポキシ樹脂の混合物であり、33質量%がマイクロカプセル化されたアミン系硬化剤、旭化成社製(商品名:HXA9322HP)。
(D-2):変性脂環式ポリアミン、T&K TOKA社製(商品名:FXR-1121)。
(E-1):N-ニトロソ-N-フェニルヒドロキシルアミンアルミニウム、富士フイルム和光純薬工業社製(商品名:Q-1301)。
(E-2):4-tert-ブチルピロカテコール、富士フイルム和光純薬工業社製(商品名:t-ブチルカテコール)。
(F-1):球状シリカ、アドマテックス社製(商品名:SE5200 SEE)。
(F-2):球状シリカ、アドマテックス社製(商品名:SE2200 SEE)。
(F-3):シリコーン複合パウダー、信越化学工業社製(商品名:KMP 600T)。
(F-4):フュームドシリカ、キャボット社製(商品名:TS-720)。
(G-1):カーボンブラック、エボニック デグサ ジャパン社製(商品名:ブラック4)。
(G-2):窒化チタン、二酸化チタン、三菱マテリアル電子化成社製(商品名:チタンブラック 13M)。
(I-1):シランカップリング剤、信越化学工業社製(商品名:KBM403;3-グリシドキシプロピルトリメトキシシラン)。
ジェットディスペンサーにて吐出した樹脂組成物について、UV硬化又は熱硬化を行い、UV硬化深度又は熱硬化時の強度の測定を行った。
<UV硬化深度>
黒色の樹脂板A(横50mm×縦25mm×厚さ1.5mm)上に、2本の耐熱テープ(厚さ100μm)を、10mmの間隔で貼った。次に、樹脂板A上の2本の耐熱テープの間に、樹脂組成物を、耐熱テープと同一の厚さの100μmとなるように塗布した。次に、樹脂板Aと、もう1つの樹脂板B(横50mm×縦25mm×厚さ1.5mm)とで、2本の耐熱テープ及び樹脂組成物を挟み、重ね合わせた2枚の樹脂板A,Bの両端をクリップで留めた。樹脂板A,Bの上部からはみ出た樹脂組成物は拭き取った。このように作製した治具の上部から、樹脂組成物に対し、UV照射を行った。より詳細には、エクセリタス・テクノロジーズ社製のUV LED照射装置「AC475(商品名)」を用いて、積算光量2000mJ/cm2で、UV照射によりUV硬化させた。積算光量は、ウシオ電機社製の「UIT-250(商品名)」の受光機「UVD-365(商品名)」を接続することで測定した。挟んでいた樹脂板A,Bの片方を剥がし、樹脂組成物の硬化物に付着した未硬化部分を取り除き、UV照射面からの硬化部分の距離を顕微鏡で測長し、その結果をUV硬化深度とした。
<熱硬化時の強度>
セラミック基板にジェットディスペンスを行った実施例及び比較例の各樹脂組成物に対して2mm×3mmのセラミックチップを載置した。次に、エクセリタス・テクノロジーズ社製のUV LED照射装置「AC475(商品名)」を用いて、積算光量2000mJ/cm2で、UV照射によりUV硬化させた。積算光量は、ウシオ電機社製の「UIT-250(商品名)」の受光機「UVD-365(商品名)」を接続することで測定した。UV硬化させた硬化性樹脂組成物を、送風乾燥機中80℃で60分間熱硬化させた。dage社製の万能型ボンドテスター「DAGE4000(商品名)」を用いて、セラミックチップに荷重をかけ、セラミックチップが剥離した時の剪断応力(N)を測定した。このような測定を1つの試験片につき10回行い、10回の平均値をシェア強度の測定値とした。測定したシェア強度が高い程、紫外線及び/又は熱による硬化性が良好であることを示す。
<評価基準>
上記のようにして硬化させた硬化物について、以下の評価基準にて評価を行った。以下の評価基準において、「◎」の評価が最も優れ、「〇」、「△」の順で評価が劣ることを示す。
◎:UV硬化深度が450μm以上、又は熱硬化時の強度が130N以上。
〇:UV硬化深度が350μm超で450um未満、又は熱硬化時の強度が60N超で130N未満。
△:UV硬化深度が350μm以下、又は熱硬化時の強度が60N以下。
以下の評価基準において、「◎」の評価が最も優れ、「〇」、「△」、「×」の順で評価が劣ることを示す。
<評価基準>
◎:連続して吐出可能なショット数が、100,000回以上。
〇:連続して吐出可能なショット数が、10,000回以上、100,000回未満。
△:連続して吐出可能なショット数が、500回以上、10,000回未満。
×:連続して吐出可能なショット数が、500回未満、又は、吐出可能な回数によらず図1(b)に示すような摺動部61あるいは衝突部62(即ち、ニードルの先端がノズルと衝突する衝突部62)においてゲル化物が発生した場合。
表1~表4に示すように、実施例1~23の吐出方法では、(A)成分としてメタクリレート化合物を含む樹脂組成物を用い、且つ、ジェットディスペンサーとして、樹脂組成物の吐出時にノズルと衝突する部材の材質が金属製のものを用いた。実施例1~23の吐出方法は、硬化性及びジェットディスペンス性の評価において共に良好な結果を示すものであった。また、実施例1~23の吐出方法は、(B)成分としてのラジカル重合開始剤の含有量が20質量%以下での硬化性を確認することができた。
50 ジェットディスペンサー
52 ニードル
54 シール(密封部材)
56 ノズル
58 チャンバー
61 摺動部
62 衝突部
S ストローク
Claims (10)
- ジェットディスペンサーを用い、当該ジェットディスペンサーのノズルから樹脂組成物を吐出する樹脂組成物の吐出方法であって、
前記ジェットディスペンサーとして、前記樹脂組成物の吐出時に前記ノズルと衝突する部材の材質が金属製のものを用い、且つ、
前記樹脂組成物が、(A)メタクリレート化合物及び(B)ラジカル重合開始剤を含む、樹脂組成物の吐出方法。 - 前記樹脂組成物が、(C)成分として、(C1)多官能チオール化合物及び(C2)アクリレート化合物のうちの少なくとも一方を更に含む、請求項1に記載の吐出方法。
- 前記樹脂組成物が、前記(C)成分として、前記(C1)多官能チオール化合物及び前記(C2)アクリレート化合物の双方を含み、前記(C1)多官能チオール化合物のチオール基の総数に対する、前記(A)メタクリレート化合物と前記(C2)アクリレート化合物の(メタ)アクリロイル基の総数の比率が、0.8~1.2である、請求項2に記載の吐出方法。
- 前記樹脂組成物が、前記(C)成分として、前記(C1)多官能チオール化合物のみを含み、前記(C1)多官能チオール化合物のチオール基の総数に対する、前記(A)メタクリレート化合物のメタクリロイル基の比率が、0.8~1.2である、請求項2に記載の吐出方法。
- 前記樹脂組成物が、(D)アニオン重合開始剤を更に含む、請求項1~4のいずれか一項に記載の吐出方法。
- 前記樹脂組成物が、(E)重合禁止剤を更に含む、請求項1~5のいずれか一項に記載の吐出方法。
- 前記樹脂組成物が、(F)フィラーを更に含む、請求項1~6のいずれか一項に記載の吐出方法。
- 前記樹脂組成物が、(G)黒色顔料を更に含む、請求項1~7のいずれか一項に記載の吐出方法。
- 請求項1~8のいずれか一項に記載の吐出方法を用いた電子部品の製造方法。
- 請求項9に記載の電子部品の製造方法によって得られた電子部品。
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