Storage method of resin composition

Abstract

To provide a storage method of a resin composition capable of keeping a temperature of the resin composition for a long time by reducing mixing of moisture into a resin composition when storing.SOLUTION: A storage method of a resin composition including at least one polymer (A) selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor includes storing a package constituted by packaging a sealed container stored with the resin composition inside, and a cooling agent with a packaging material, wherein the sealed container has a moisture percentage change of a content of 0.005% / day or less, the cooling agent has a phase change temperature from a solid of -18°C or lower, and the packaging material has a heat-transfer rate of 0.050 W / (m.K) or lower.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a method for storing a resin composition. [Background technology]

[0002] In recent years, three-dimensional packaging of semiconductor chips has been considered to improve the integration density of LSIs (Large Scale Integrated Circuits).When three-dimensional packaging of semiconductor chips is performed by C2W (Chip-to-Wafer) bonding, the use of hybrid bonding technology used in W2W (Wafer-to-Wafer) bonding to perform fine bonding of wiring between devices is being considered.

[0003] In C2W hybrid bonding, there is a risk of misalignment due to the thermal expansion of the substrate, chip, etc. caused by heating during bonding. To address this issue, Patent Document 1 discloses an example of a technology that can lower the bonding temperature by using a cyclic olefin resin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2019-204818 A Summary of the Invention [Problem to be solved by the invention]

[0005] When three-dimensionally mounting semiconductor chips by C2W (Chip-to-Wafer) bonding, W2W (Wafer-to-Wafer) bonding, etc., substrates having an electrode layer containing copper and an insulating film that is a cured product obtained by curing a resin composition are bonded to each other, or the substrate is bonded to a chip having an electrode layer and an insulating film. A resin composition containing a polyimide precursor, etc. is used for C2W bonding, W2W bonding, and other applications requiring heat resistance, etc.

[0006] Resin compositions containing polyimide precursors and the like may be subject to quality deterioration due to inclusion of moisture, exposure to temperature changes, etc. Therefore, it is desirable to reduce inclusion of moisture into the resin composition during storage, such as during transportation, and to be able to maintain the temperature of the resin composition for a long period of time.

[0007] The present disclosure has been made in consideration of the above, and aims to provide a method for storing a resin composition that reduces the inclusion of moisture in the resin composition during storage and can maintain the temperature of the resin composition for a long period of time. [Means for solving the problem]

[0008] Specific means for achieving the above object are as follows. <1> A method for storing a resin composition containing at least one polymer (A) selected from the group consisting of polyimide, a polyimide precursor, a polybenzoxazole, and a polybenzoxazole precursor, comprising the steps of: The method includes storing a package obtained by packaging a sealed container in which the resin composition is stored and a coolant in a packaging material, The sealed container has a moisture content change of 0.005% / day or less; The coolant has a phase change temperature from a solid of −18° C. or lower; The packaging material has a heat transfer coefficient of 0.050 W / (m·K) or less. <2> The polymer (A) contains the polyimide precursor, The polyimide precursor contains a compound having a structural unit represented by the following general formula (1): <1> A method for storing the resin composition according to claim 1.

[0009] [ka] In the general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R 6 and R 7 each independently represents a hydrogen atom or a monovalent organic group. <3> In the general formula (1), the R 6 and the above R 7 The monovalent organic group in the formula (2) is any one of an ethyl group, an isobutyl group, and a t-butyl group. <2> A method for storing the resin composition according to claim 1.

[0010] [ka]

[0011] In general formula (2), R 8 ~R 10 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; R x represents a divalent linking group. <4> Store the packaged items at -20°C to -30°C and a relative humidity of 0% to 95%. <1> ~ <3> 13. A method for storing a resin composition according to any one of the above items. <5> A method for storing a resin composition containing at least one polymer (A) selected from the group consisting of polyimide, a polyimide precursor, a polybenzoxazole, and a polybenzoxazole precursor, comprising the steps of: A method for storing a resin composition, comprising storing the resin composition in a sealed container in which the resin composition is stored and the change in moisture content is 0.005% / day or less under conditions of -20°C to 30°C and a relative humidity of 0% to 95%. Effect of the Invention

[0012] According to the present disclosure, it is possible to provide a method for storing a resin composition that reduces the inclusion of moisture in the resin composition during storage and can maintain the temperature of the resin composition for a long period of time. [Brief description of the drawings]

[0013] [Figure 1] FIG. 2 is a schematic cross-sectional view showing an example of a package. [Diagram 2] FIG. 11 is a schematic plan view showing another example of a package. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Hereinafter, the embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to the numerical values ​​and their ranges, and do not limit the present disclosure.

[0015] In the present disclosure, "A or B" may include either A or B, or may include both. In the present disclosure, the term "step" includes not only a step that is independent of other steps, but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In the present disclosure, a numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple types of corresponding substances. When multiple types of substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, when a functional group has a substituent, the number of carbon atoms in the functional group means the total number of carbon atoms including the number of carbon atoms in the substituent.

[0016] [Method of storing resin composition] The resin composition disclosed herein is a method for storing a resin composition comprising at least one polymer (A) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor, the method including storing a package obtained by packaging, in a packaging material, a sealed container in which the resin composition is stored and a coolant, wherein the sealed container has a moisture content change of 0.005% / day or less, the coolant has a phase change temperature from solid of -18°C or less, and the packaging material has a heat transfer coefficient of 0.050 W / (m·K) or less.

[0017] The resin composition storage method of the present disclosure is a method for storing a package obtained by packaging a sealed container containing a resin composition together with a coolant in a packaging material, and the sealed container, coolant, and packaging material satisfy the above-mentioned conditions. This reduces the intrusion of moisture into the resin composition during storage, and makes it possible to maintain the temperature of the resin composition for a long period of time (for example, the resin composition can be stored at a low temperature for a long period of time using the coolant).

[0018] (sealed container) The sealed container is a container for storing the resin composition. The sealed container has a moisture content change of 0.005% / day or less, so that it is possible to prevent moisture from entering the resin composition stored therein from the outside of the sealed container.

[0019] The change in moisture content of the sealed container may be 0.004% / day or less, or may be 0.003% / day or less. The lower limit of the change in moisture content of the sealed container is not particularly limited, and may be 0% / day or 0.00001% / day or more.

[0020] The change in moisture content of the sealed container can be measured as follows. The container in which the moisture content is measured is filled with the solvent used in the resin composition at a volume of 95% or more relative to the container volume, and left to stand for 48 hours under conditions of temperature conditions of 20° C. to 23° C. and relative humidity of 80% to 95%. The moisture content before and after leaving it to stand for 48 hours is compared to calculate the change in moisture content per day.

[0021] The sealed container is not particularly limited as long as it can seal the resin composition stored therein from the outside air and satisfies the above-mentioned moisture permeability. The shape of the sealed container is not particularly limited, and may be a bottle shape, a box shape, a bag shape, or the like.

[0022] The material of the sealed container may be plastic, metal, ceramic, glass, or a combination thereof. The sealed container may be a light-blocking container.

[0023] The airtight container may be a bottle with a lid or an inner lid. For example, the airtight container may be a clean bottle, such as a clean bottle manufactured by Aicello Corporation.

[0024] The resin composition is supplied into a sealed container and stored in a sealed state. At this time, the sealed container in which the resin composition is stored is stored in a state where it is packed in a packaging material together with a coolant. The sealed container and the coolant may each be independently packed in a plurality of packaging materials, and in particular, a plurality of sealed containers may be packed in a packaging material.

[0025] The volume of the resin composition stored in one sealed container is not particularly limited and may be, for example, 10 mL to 30 L, 50 mL to 2 L, or 100 mL to 1 L.

[0026] (coolant) The coolant has a phase change temperature from a solid of −18° C. or lower. By using such a coolant, the temperature of the resin composition can be maintained for a long period of time.

[0027] Examples of cooling agents include dry ice and ice packs whose solid-to-phase change temperature is -18°C or lower.

[0028] The ratio of the volume of the coolant to the volume of the resin composition stored in the sealed container (volume of coolant / volume of resin composition) may be 2-8. When multiple sealed containers are packed in packaging material, the volume of the resin composition stored in the sealed containers may be read as "the total volume of the resin composition stored in the multiple sealed containers." When multiple coolants are packed in packaging material, the volumetric percentage of the coolants may be read as the "total volumetric percentage of the coolants."

[0029] (Packing materials) The packaging material is a component that packs the sealed container in which the resin composition is stored and the coolant. The heat transfer coefficient of the packaging material is 0.050 W / (m K) or less. By using such a packaging material, the temperature of the resin composition can be maintained for a long period of time.

[0030] From the viewpoint of maintaining the temperature of the resin composition at a low temperature for a long period of time, the heat transfer coefficient of the packaging material may be 0.045 W / (m·K) or less, 0.040 W / (m·K) or less, or 0.035 W / (m·K) or less. The lower limit of the heat transfer rate of the packaging material is not particularly limited, and may be, for example, 0.05 W / (m·K) or more.

[0031] Examples of packaging materials include insulating materials such as polystyrene foam, urethane foam, polyethylene foam, and phenol foam.

[0032] The thickness of the packaging material may be 5 cm or more, or may be 3 cm to 10 cm.

[0033] If the coolant includes a coolant that changes phase from a solid to a gas, such as dry ice, the packaging may be provided with an opening to allow the gas to escape.

[0034] In a package obtained by packaging a sealed container in which a resin composition is stored and a coolant in a packaging material, the ratio of the total volume of the sealed container and the coolant to the volume of the package may be 50% by volume to 90% by volume.

[0035] The conditions for storing the above-mentioned package are not particularly limited as long as they are within the range in which inclusion of moisture in the resin composition can be reduced and the temperature of the resin composition can be maintained for a long period of time. For example, the storage temperature may be -20° C. to 30° C., and the relative humidity may be 0% to 95%. The storage time may be, for example, one day or less, or may be 2 hours to 2 days.

[0036] As a method for storing the resin composition, the packaged product may be stored under the above-mentioned conditions, or the sealed container in which the resin composition is stored may be stored under the above-mentioned conditions.

[0037] The package may be stored under the above conditions at a specific location, or may be stored under the above conditions while being transported.

[0038] An example of the package is shown in Figures 1 and 2. Note that the package is not limited to Figures 1 and 2. As shown in Figure 1, multiple bottles (sealed containers in which a resin composition is stored) may be placed in a polystyrene foam body via a pressing plate, and dry ice may be placed on the multiple bottles. Then, the polystyrene foam body may be sealed with a polystyrene foam lid. Alternatively, as shown in Fig. 2, a plurality of packaged bottles (sealed containers in which the resin composition is stored) and dry ice may be placed in a polystyrene foam body, and the polystyrene foam body may be sealed with a polystyrene foam lid (not shown). In this case, the bottles may be packaged using polystyrene foam or other packaging materials.

[0039] (Resin composition) The resin composition stored in the sealed container contains at least one type of polymer (A) (hereinafter also referred to as "component (A)") selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor.

[0040] The resin composition of the present disclosure can be used, for example, in hybrid bonding applications such as C2W (Chip-to-Wafer) bonding and W2W (Wafer-to-Wafer) bonding, and in applications for forming adhesive layers, insulating layers, rewiring insulating layers, and the like.

[0041] The polymer (A) may be a single polymer or a combination of two or more polymers. For example, the polymer (A) may be a single polyimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor, or a combination of polyimide and polyimide precursor, or a combination of polybenzoxazole and polybenzoxazole precursor.

[0042] <Polyimide> The polyimide is not particularly limited as long as it is a polymeric compound having a plurality of structural units including imide bonds, and preferably includes, for example, a compound having a structural unit represented by the following general formula (X), which tends to provide an insulating film with high reliability.

[0043] [ka]

[0044] In formula (X), X represents a tetravalent organic group, and Y represents a divalent organic group. Preferred examples of the substituents X and Y in formula (X) are the same as the preferred examples of the substituents X and Y in formula (1) described later. The polyimide may have a plurality of structural units represented by the above general formula (X), and X and Y in the plurality of structural units may be the same or different.

[0045] <Polyimide precursor> The polyimide precursor means a compound corresponding to either a polyamic acid or a compound in which at least a part of hydrogen atoms of carboxyl groups in a polyamic acid is substituted with a monovalent organic group. The polyimide precursor preferably contains a polyimide precursor having a polymerizable unsaturated bond.

[0046] The polyimide precursor preferably contains a compound having a structural unit represented by the following general formula (1), which tends to provide an insulating film with high reliability.

[0047] [ka]

[0048] In the general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. 6 and R 7 each independently represents a hydrogen atom or a monovalent organic group. The polyimide precursor may have a plurality of structural units represented by the above general formula (1), and X, Y, and R in the plurality of structural units 6 and R 7 may be the same or different. In addition, R 6 and R 7 are each independently a hydrogen atom or a monovalent organic group, the combination of which is not particularly limited. For example, R 6 and R 7 may each be a hydrogen atom, one may be a hydrogen atom and the other may be a monovalent organic group described later, or both may be the same or different monovalent organic groups. 6 and R 7 The combinations may be the same or different.

[0049] In general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group represented by X may contain an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon groups (e.g., aromatic rings having 6 to 20 carbon atoms) and aromatic heterocyclic groups (e.g., heterocyclic rings having 5 to 20 atoms). The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, and a phenanthrene ring. When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of the substituent of the aromatic ring include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, and an amino group. When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains one to four benzene rings, more preferably contains one to three benzene rings, and even more preferably contains one or two benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, the benzene rings may be linked by a single bond or by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si(R A ) 2 - 2 R A each independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(R B ) 2 -O-) n ;Two R's B each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more.) or a composite linking group combining at least two of these linking groups. In addition, two benzene rings may be linked at two positions by at least one of a single bond and a linking group to form a 5- or 6-membered ring containing a linking group between the two benzene rings.

[0050] In the general formula (1), when the tetravalent organic group represented by X contains a benzene ring, -COOR 6The -CONH- group and the -COOR- group are preferably in the ortho position relative to each other. 7 The group and the -CO- group are preferably in the ortho position relative to each other.

[0051] Specific examples of the tetravalent organic group represented by X include groups represented by the following formulae (A) to (F). Among them, from the viewpoint of obtaining an insulating film excellent in flexibility, a group represented by the following formula (E) is preferred, and in the following formula (E), C is more preferably a group containing an ether bond, and further preferably an ether bond. The following formula (F) is a structure in which C in the following formula (E) is a single bond. It should be noted that the present disclosure is not limited to the following specific examples.

[0052] [ka]

[0053] In formula (D), A and B are each independently a single bond or a divalent group that is not conjugated with a benzene ring. However, A and B cannot both be single bonds. Examples of divalent groups that are not conjugated with a benzene ring include a methylene group, a halogenated methylene group, a halogenated methylmethylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si(R A ) 2 - 2 R A each independently represents a hydrogen atom, an alkyl group, or a phenyl group.) Among these, A and B each independently preferably represent a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, or the like, and more preferably an ether bond.

[0054] In formula (E), C is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-OC(=O)-), a silylene bond (-Si(R A ) 2 - 2 RA each independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(R B ) 2 -O-) n ;Two R's B each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more.) or a divalent group combining at least two of these. C preferably contains an ether bond, and is preferably an ether bond. Furthermore, C may be a structure represented by the following formula (C1).

[0055] [ka]

[0056] The alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms.

[0057] In general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 12 to 18 carbon atoms. The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group. Examples of the divalent aromatic group include a divalent aromatic hydrocarbon group (e.g., an aromatic ring having 6 to 20 carbon atoms) and a divalent aromatic heterocyclic group (e.g., a heterocyclic ring having 5 to 20 atoms), and the like, with a divalent aromatic hydrocarbon group being preferred.

[0058] Specific examples of the divalent aromatic group represented by Y include groups represented by the following formulae (G) to (I). Among them, from the viewpoint of obtaining an insulating film excellent in flexibility, a group represented by the following formula (H) is preferred, and in the following formula (H), D is more preferably a group containing an ether bond, and further preferably an ether bond.

[0059] [ka]

[0060] In formulae (G) to (I), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group or a halogen atom, and n each independently represents an integer of 0 to 4. In formula (H), D is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-OC(=O)-), a silylene bond (-Si(R A ) 2 - 2 R A each independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(R B ) 2 -O-) n ;Two R's B Each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more.) or a divalent group combining at least two of them. D may be a structure represented by the above formula (C1). Specific examples of D in formula (H) are the same as specific examples of C in formula (E). D in formula (H) is preferably an ether bond, a group containing an ether bond and a phenylene group, a group containing an ether bond, a phenylene group and an alkylene group, or the like.

[0061] The alkyl group represented by R in formulas (G) to (I) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of the alkyl group represented by R in formulae (G) to (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

[0062] The alkoxy group represented by R in formulas (G) to (I) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms. Specific examples of the alkoxy group represented by R in formulas (G) to (I) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, and a t-butoxy group.

[0063] The halogenated alkyl group represented by R in formulas (G) to (I) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and further preferably a halogenated alkyl group having 1 or 2 carbon atoms. Specific examples of the halogenated alkyl group represented by R in the formulae (G) to (I) include alkyl groups in which at least one hydrogen atom contained in the alkyl group represented by R in the formulae (G) to (I) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, etc. are preferred.

[0064] In formulae (G) to (I), n is preferably 0 to 2, more preferably 0 or 1, and further preferably 0.

[0065] Specific examples of the divalent aliphatic group represented by Y include a linear or branched alkylene group, a cycloalkylene group, a divalent group having a polyalkylene oxide structure, and a divalent group having a polysiloxane structure.

[0066] The group represented by formula (I) is preferably a group represented by the following formula (I').

[0067] [ka]

[0068] In formula (I'), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0069] The divalent organic group represented by Y may be, for example, a group represented by the following formulae (J) to (M).

[0070] [ka]

[0071] In the general formula (1), the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y is not particularly limited. Examples of the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y include a combination of X being a group represented by formula (E) and Y being a group represented by formula (H); a combination of X being a group represented by formula (E) and Y being a group represented by formula (I); a combination of X being a group represented by formula (E) and Y being a group represented by formula (G) and a group represented by formula (H), and the like.

[0072] R 6 and R 7each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably any one of a group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, and further preferably contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2), and particularly preferably contains a group represented by the following general formula (2). In particular, when the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the i-ray transmittance is high, and a good cured product tends to be formed even when cured at a low temperature of 400°C or less. Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group, and among these, an ethyl group, an isobutyl group, and a t-butyl group are preferred.

[0073] [ka]

[0074] In general formula (2), R 8 ~R 10 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; R x represents a divalent linking group.

[0075] R in general formula (2) 8 ~R 10 The aliphatic hydrocarbon group represented by the formula (I) has 1 to 3 carbon atoms, and preferably 1 or 2. 8 ~R 10 Specific examples of the aliphatic hydrocarbon group represented by the formula include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc., with a methyl group being preferred.

[0076] R in general formula (2) 8 ~R 10 The combination of R 8 and R 9 is a hydrogen atom, and R 10is preferably a hydrogen atom or a methyl group.

[0077] R in general formula (2) x is a divalent linking group, and is preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include linear or branched alkylene groups. R x The number of carbon atoms in is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 or 3.

[0078] In the general formula (1), R 6 and R 7 At least one of R is preferably a group represented by the general formula (2). 6 and R 7 It is more preferable that both of the above are a group represented by the general formula (2).

[0079] When the component (A) contains a compound having a structural unit represented by the above-mentioned general formula (1), R 6 and R 7 R which is a group represented by general formula (2) 6 and R 7 The proportion is preferably 60 mol % or more, more preferably 70 mol % or more, and even more preferably 80 mol % or more. There is no particular upper limit, and it may be 100 mol %. The above ratio may be 0 mol % or more and less than 60 mol %.

[0080] The group represented by general formula (2) is preferably a group represented by the following general formula (2').

[0081] [ka]

[0082] In general formula (2'), R 8 ~R 10each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; and q represents an integer of 1 to 10.

[0083] In formula (2′), q is an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 2 or 3.

[0084] The content of the structural unit represented by general formula (1) contained in the compound having the structural unit represented by general formula (1) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, based on the total structural units. The upper limit of the content is not particularly limited, and may be 100 mol%.

[0085] When the component (A) is a polyimide or a polyimide precursor, it may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in the general formula (X) or general formula (1), X corresponds to a residue derived from a tetracarboxylic dianhydride, and Y corresponds to a residue derived from a diamine compound. The component (A) may be synthesized using a tetracarboxylic acid instead of a tetracarboxylic dianhydride. In addition, a group represented by the general formula (2) or a group represented by the general formula (2)' may be introduced into the polyimide precursor using a compound represented by R-OH.

[0086] <Polybenzoxazole> Polybenzoxazole refers to a polymer containing a benzoxazole structure in the structural unit. The polybenzoxazole preferably contains a compound having a structural unit represented by the following general formula (Z-1).

[0087] JPEG2025022639000012.jpg43164

[0088] In formula (Z-1), U represents a single bond or a divalent linking group, and W represents a divalent linking group. Polybenzoxazole may have a plurality of structural units represented by the above general formula (Z-1), and U and W in the plurality of structural units may be the same or different.

[0089] Polybenzoxazole can be obtained, for example, by a cyclization reaction (condensation polymerization reaction) between a dicarboxylic acid and a diaminodihydroxy compound. The dicarboxylic acid is not particularly limited, and examples thereof include terephthalic acid (benzene-1,4-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid), phthalic acid (benzene-1,2-dicarboxylic acid), 4,4'-dicarboxybiphenylmethane, 4,4'-dicarboxybiphenyl ether, 4,4'-dicarboxybiphenyl, and 2,2-(4,4'-dicarboxybiphenyl)propane. The diaminodihydroxy compound is not particularly limited, and examples thereof include 1,3-diamino-4,6-dihydroxybenzene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenylmethane, and 2,2-(3,3'-diamino-4,4'-dihydroxydiphenyl)propane.

[0090] <Polybenzoxazole precursor> The polybenzoxazole precursor is a polyhydroxyamide, and preferably contains, for example, a compound having a structural unit represented by the following general formula (Z-2): This tends to provide an insulating film with high reliability.

[0091] [ka]

[0092] In formula (Z-2), U represents a single bond or a divalent linking group, and W represents a divalent linking group. The polybenzoxazole precursor may have a plurality of structural units represented by the above general formula (Z-2), and U and W in the plurality of structural units may be the same or different.

[0093] The polybenzoxazole precursor can be obtained, for example, by a condensation polymerization reaction between a dicarboxylic acid and a diaminodihydroxy compound. Examples of the dicarboxylic acid and the diaminodihydroxy compound include the dicarboxylic acid and the diaminodihydroxy compound exemplified in the above-mentioned section on polybenzoxazole.

[0094] There are no particular limitations on the molecular weight of the component (A), and for example, the weight average molecular weight is preferably 10,000 to 200,000, and more preferably 10,000 to 100,000. The weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be calculated using a standard polystyrene calibration curve.

[0095] The resin composition may contain a resin component other than the component (A). For example, from the viewpoint of heat resistance, the resin composition may contain other resins such as novolac resin, acrylic resin, polyethernitrile resin, polyethersulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyvinyl chloride resin, etc. The other resins may be used alone or in combination of two or more.

[0096] In the resin composition, the content of component (A) relative to the total amount of resin components is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.

[0097] The resin composition may contain other components in addition to the component (A), such as the resin components other than the component (A), polymerizable monomers, nitrogen-containing organosilicon compounds, photopolymerization initiators, thermal polymerization initiators, solvents, sensitizers, stabilizers, coupling agents, surfactants, thermal base generators, photobase generators, leveling agents, photosensitizers, and rust inhibitors. The resin composition may contain, as other components, a solvent, a coupling agent, etc. In particular, when a material that deteriorates due to a reaction or the like in the presence of moisture is used, such as a silane coupling agent, the storage method of the resin composition of the present disclosure is particularly useful because the inclusion of moisture in the resin composition can be suppressed by the storage method of the resin composition of the present disclosure.

[0098] (Solvent (B)) The resin composition of the present disclosure may contain a solvent (B) (hereinafter also referred to as "component (B)"). Examples of component (B) include the following compounds from the viewpoint of reducing the reproductive toxicity and environmental load of the resin composition. The component (B) may be used alone or in combination of two or more types.

[0099] [ka]

[0100] The component (B) contained in the resin composition of the present disclosure is not limited to the above-mentioned compounds, and may be other solvents. The component (B) may be an ester solvent, an ether solvent, a ketone solvent, a hydrocarbon solvent, an aromatic hydrocarbon solvent, a sulfoxide solvent, or the like. Preferable examples of the solvent for component (B) include γ-butyrolactone, cyclopentanone, and ethyl lactate.

[0101] In the resin composition of the present disclosure, from the viewpoint of reducing toxicity such as reproductive toxicity, the content of NMP may be 1 mass % or less based on the total amount of the resin composition, and may be 3 mass % or less based on the total amount of the (A) component.

[0102] In the resin composition of the present disclosure, the content of the component (B) is preferably 50 parts by mass to 10,000 parts by mass per 100 parts by mass of the component (B).

[0103] (Coupling Agent) The resin composition of the present disclosure may contain a coupling agent. The coupling agent reacts with the (A) component to crosslink or the coupling agent itself polymerizes during heat treatment. This tends to further improve the adhesion between the obtained cured product and the substrate.

[0104] Specific examples of the coupling agent are not particularly limited. Examples of the coupling agent include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidine, and the like. Silane coupling agents such as lysinopropyl silane, diethoxy-3-glycidoxypropyl methyl silane, N-(3-diethoxymethylsilylpropyl) succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyl trimethoxy silane, N,N'-bis(2-hydroxyethyl)-3-aminopropyl triethoxy silane, and 3-ureidopropyl triethoxy silane; aluminum-based adhesion aids such as aluminum tris(ethyl acetoacetate), aluminum tris(acetylacetonate), and ethyl acetoacetate aluminum diisopropylate; and the like. The coupling agents may be used alone or in combination of two or more.

[0105] When the resin composition of the present disclosure contains a coupling agent, the content of the coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of component (A). In the resin composition of the present disclosure, the content of the coupling agent may be 0.5 parts by mass or less, 0.3 parts by mass or less, or 0.1 parts by mass or less, relative to 100 parts by mass of the component (A). EXAMPLES

[0106] The present disclosure will be described in more detail below with reference to examples and comparative examples. Note that the present disclosure is not limited to the following examples.

[0107] [Preparing airtight containers, coolants and packaging materials] The following airtight containers, coolants, and packaging materials were prepared. (sealed container) Airtight container 1: Clean bottle (Aicello Co., Ltd., moisture content change: 0.0001 / day or less, capacity: 1L) Airtight container 2: Clean bottle (Aicello Co., Ltd., moisture rate change: 0.0001 / day or less, capacity: 4L) Airtight container 3: Eye Boy (As One Corporation, moisture rate change: 0.01% / day, capacity: 1L) (coolant) Coolant 1: Dry ice (phase change temperature from solid: -79°C, density: 1.566g / cm 3 , Usage amount: 1.0kg) Coolant 2: Ice (phase change temperature from solid: 0°C, density: 0.917g / cm 3 , Usage amount: 1.0kg) (Packing materials) Packaging material 1: Styrofoam (heat transfer coefficient: 0.045 W / (m K), thickness: 3 cm, capacity: 10 L) Packaging material 2: Cardboard (heat transfer coefficient: 0.070 W / (m K), thickness: 0.5 cm, capacity: 10 L)

[0108] [Preparation of Resin Compositions 1 to 3] First, polymers A1 to A3 were obtained as shown in the following Synthesis Examples 1 to 3.

[0109] (Synthesis Example 1) 62g of 3,3',4,4'-biphenylethertetracarboxylic dianhydride (ODPA) and 36g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) were dissolved in 915g of 3-methoxy-N,N-dimethylpropanamide. The resulting solution was stirred at 30°C for 4 hours and then at room temperature overnight to obtain polyamic acid. 78g of trifluoroacetic anhydride and 109g of 2-hydroxyethyl methacrylate (HEMA) were added thereto at room temperature and stirred at 45°C for 10 hours. This reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor A1 (hereinafter referred to as polymer A1). The weight average molecular weight of polymer A1 was determined by gel permeation chromatography (GPC) in terms of standard polystyrene. The weight average molecular weight of polymer A1 was 24000. Specifically, a solution in which 0.5 mg of A1 was dissolved in 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] was used, and the measurement was performed under the following conditions. -Measurement conditions- Measuring device: Shimadzu Corporation SPD-M20A Pump: Shimadzu Corporation LC-20AD Column oven: Shimadzu Corporation: CTO-20A Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF=1 / 1 (volume ratio) LiBr(0.03mol / L), H 3 PO 4 (0.06mol / L) Flow rate: 1.0 mL / min, detector: UV 270 nm, column temperature: 40°C Standard polystyrene: Calibration curves created using Tosoh TSKgel standard Polystyrene Types F-1, F-4, F-20, F-80, and A-2500

[0110] <Esterification rate> The esterification ratio of polymer A1 (the ratio of ester groups reacted with HEMA to the total of ester groups reacted with HEMA and carboxy groups unreacted with HEMA) was calculated by performing NMR measurement under the following conditions: The esterification ratio was 79 mol%, and the ratio of unreacted carboxy groups was 21 mol%. -Measurement conditions- Measurement equipment: Bruker Biospin AV400M Magnetic field strength: 400MHz Reference material: Tetramethylsilane (TMS) Solvent: Dimethyl sulfoxide (DMSO)

[0111] (Synthesis Example 2) In a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid and 90 g of N-methyl-2-pyrrolidone were charged, and the flask was cooled to 5°C, after which 12.64 g of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4'-diphenyl ether dicarboxylic acid chloride. Next, in a 0.5-liter flask equipped with a stirrer and a thermometer, 87.5 g of N-methyl-2-pyrrolidone was charged, and 18.30 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added and stirred to dissolve. Next, 8.53 g of pyridine was added, and while maintaining the temperature at 0 to 5°C, a solution of 4,4'-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, and stirring was continued for 30 minutes. The obtained solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain polyhydroxyamide (polybenzoxazole precursor, hereinafter referred to as polymer A2). The weight average molecular weight of polymer A2 was determined by GPC method using standard polystyrene. The weight average molecular weight of polymer A2 was 15,000.

[0112] [Synthesis Example 3] In a 0.5 liter flask equipped with a stirrer and a thermometer, 4.1 g of 4,4'-diphenyl ether dicarboxylic acid, 2.7 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bispropylamine, 60 g of 3-methoxy-N,N-dimethylpropionamide, and 0.01 g of ion-exchanged water were charged and stirred for 30 minutes. 3.5 g of BTDA (3,3',4,4'-benzophenonetetracarboxylic dianhydride) and 2.4 g of PMDA (pyromellitic dianhydride) were added to the flask and dissolved by stirring. The temperature in the flask was raised to 75°C and stirring was continued for 14 hours. The resulting solution was filtered to obtain a polyimide precursor A3 (hereinafter referred to as polymer A3).

[0113] Resin compositions of each Example and Comparative Example were prepared by mixing the components shown below in the ratios shown in Table 1. The numerical values ​​of each component in Table 1 indicate the parts by mass of each component used when preparing the resin composition. Polymer (A) A1, A2 and A3 above ·solvent B1: 3-Methoxy-N,N-dimethylpropionamide B2: γ-butyrolactone (GBL) Polymerizable monomers C1: Tetraethylene glycol dimethacrylate (TEGDMA) C2: 4,4'-(1,1,1,3,3,3-hexafluoropropane-2,2-diyl)bis[2,6-bis(hydroxymethyl)phenol] Rust inhibitor D1: 1,2,3-benzotriazole Photosensitizer E1: 2-(ethoxycarbonyloxyimino)-1-phenylpropan-1-one E2: 4,4′-bis(diethylamino)benzophenone E3: TPPA-528 (CAS137902-98-8) Adhesion aid F1:UCT803 F2:SIB1140.0

[0114] [Table 1]

[0115] [Examples 1 to 6 and Comparative Examples 1 to 3] The above-mentioned sealed container, coolant, and packaging material, as well as the above-mentioned resin composition, were combined as shown in Table 2, and a package was prepared by packaging the sealed container in which the resin composition was stored and the coolant in the packaging material. The packages prepared in each of the Examples and Comparative Examples are shown in Table 2. In Table 2, the parts and components that were used are marked with a circle, and the parts and components that were not used are marked with a -. In each of the Examples and Comparative Examples, the resin composition was used in an amount of 95% by volume relative to the capacity of the sealed container.

[0116] [Evaluation of moisture changes] For the packages prepared in each of the Examples and Comparative Examples, the moisture content in the resin composition was evaluated under the following conditions. Specifically, the moisture content was measured using a Karl Fischer moisture meter. The evaluation criteria for moisture change are as follows. The results are shown in Table 2. -Evaluation criteria- A The amount of moisture mixed in after 48 hours of storage was 0.01% by mass or less. B The amount of moisture contained in the product after 48 hours of storage exceeded 0.01% by mass.

[0117] [Evaluation of temperature changes] For the packages prepared in each of the Examples and Comparative Examples, the temperature change inside the packages was evaluated under the following conditions. Specifically, the evaluation was carried out indoors at a room temperature of 21°C and humidity of 75-85%. A cooling material was placed inside the packaging material, and a recording thermometer was attached to the wall of the packaging material at a distance of at least 10 cm from the cooling material and at least 5 cm from the bottom of the packaging material. The packaging material was then sealed as tightly as possible with commercially available cloth adhesive tape, and the temperature change over time was measured. The evaluation criteria for temperature change are as follows. The results are shown in Table 2. -Evaluation criteria- A The temperature inside the package was below 0°C for 10 hours after storage, and there was no change in the strength of the packaging material. B After 10 hours of storage, the temperature inside the package exceeded 0°C and the strength of the packaging material had decreased.

[0118] [Table 2]

[0119] As shown in Table 2, in Examples 1 to 6, the inclusion of moisture in the resin composition during storage was reduced, and the temperature of the resin composition could be maintained for a long period of time.

Claims

1. A method for storing a resin composition comprising at least one polymer (A) selected from the group consisting of polyimide, a polyimide precursor, a polybenzoxazole, and a polybenzoxazole precursor, comprising the steps of: The method includes storing a package obtained by packaging a sealed container in which the resin composition is stored and a coolant in a packaging material, The sealed container has a moisture content change of 0.005% or less per day; The coolant has a phase change temperature from a solid of −18° C. or lower; The method for storing a resin composition, wherein the packaging material has a heat transfer coefficient of 0.050 W / (m·K) or less.

2. The polymer (A) contains the polyimide precursor, The method for storing a resin composition according to claim 1 , wherein the polyimide precursor contains a compound having a structural unit represented by the following general formula (1): 【Chemistry 1】 In the general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, R ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group.

3. In the general formula (1), the R ６ and the R ７ The method for storing a resin composition according to claim 2, wherein the monovalent organic group is any one of a group represented by the following general formula (2), an ethyl group, an isobutyl group, and a t-butyl group: 【Chemistry 2】 In general formula (2), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; R ｘ represents a divalent linking group.

4. The method for storing a resin composition according to any one of claims 1 to 3, wherein the package is stored under conditions of -20°C to 30°C and a relative humidity of 0% to 95%.

5. A method for storing a resin composition comprising at least one polymer (A) selected from the group consisting of polyimide, a polyimide precursor, a polybenzoxazole, and a polybenzoxazole precursor, comprising the steps of: The resin composition is stored in a sealed container in which the resin composition is stored and in which the change in moisture content is 0.005% / day or less, under conditions of -20°C to 30°C and a relative humidity of 0% to 95%.

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