Composition for curing resin, cured product of the composition, method for producing the composition and the cured product, and semiconductor device
阅读说明：本技术 固化树脂用组合物、该组合物的固化物、该组合物及该固化物的制造方法、以及半导体装置 (Composition for curing resin, cured product of the composition, method for producing the composition and the cured product, and semiconductor device ) 是由 西谷佳典 佐藤树生 南昌树 于 2019-08-01 设计创作，主要内容包括：本发明提供一种用于得到高耐热性固化物的快速固化性优异的固化树脂用组合物、其固化物、以及该固化树脂用组合物和该固化物的制造方法。此外,提供一种将上述固化物作为密封材料使用的半导体装置。本发明的固化树脂用组合物含有(A)多官能苯并嗪化合物、(B)具有至少一个降冰片烷结构和至少两个环氧基的多官能环氧化合物、(C)固化剂、(D)作为二氮杂双环烯烃的双酚盐的固化促进剂,其中,上述(A)多官能苯并嗪化合物具有至少两个苯并嗪环,且为选自具有式(1)的结构单元的多官能苯并嗪化合物和式(2)的结构所示的多官能苯并嗪化合物中的至少1种。(The invention provides a composition for a cured resin with excellent rapid curing property for obtaining a cured product with high heat resistance, a cured product thereof, the composition for the cured resin and a method for manufacturing the cured product. Further, there is provided a method of using the cured product as a sealing materialA semiconductor device for use in the semiconductor device. The curable resin composition of the present invention contains (A) a polyfunctional benzene compound An oxazine compound, (B) a polyfunctional epoxy compound having at least one norbornane structure and at least two epoxy groups, (C) a curing agent, and (D) a curing accelerator which is a bisphenolate salt of a diazabicycloalkene, wherein the (A) polyfunctional benzo group The oxazine compound having at least two benzo groups Oxazine ring and is selected from multifunctional benzo having structural unit of formula (1) An oxazine compound and a multifunctional benzo represented by the structure of formula (2))
1. A composition for curing a resin, comprising:
(A) multifunctional benzoOxazine compounds, the multifunctional benzolsThe oxazine compound having at least two benzo groupsOxazine ring and is selected from multifunctional benzo having structural unit of formula (1)An oxazine compound and a multifunctional benzo represented by the structure of formula (2)At least 1 of the oxazine compounds,
(B) a polyfunctional epoxy compound having at least one norbornane structure and at least two epoxy groups,
(C) a curing agent for curing the epoxy resin composition,
(D) a cure accelerator which is a bisphenolate of a diazabicycloalkene;
in the formula (1), R represents a chain alkyl group having 1-12 carbon atoms, a cyclic alkyl group having 3-8 carbon atoms, or an aryl group having 6-14 carbon atoms, the aryl group may have a halogen or a chain alkyl group having 1-12 carbon atoms as a substituent, Z represents hydrogen, a hydrocarbon group having 1-8 carbon atoms and/or a linking group, each of which may be the same or different, and at least one is a linking group, benzoThe oxazine rings are linked to each other through the linking group;
in the formula (2), L is a 2-valent organic group having 1 to 5 aromatic rings or an alkylene group having 1 to 10 carbon atoms, and the organic group and the alkylene group may contain oxygen and/or sulfur.
2. The composition for curing resin according to claim 1, wherein the (D) curing accelerator is represented by the structure of formula (9) or formula (10),
in the formula (9), R is alkylene which may have a substituent, carbonyl, sulfonyl or thioether bond;
in the formula (10), R is an alkylene group which may have a substituent, a carbonyl group, a sulfonyl group or a thioether bond.
3. The composition for curing resin according to claim 1 or 2, further comprising (E) an inorganic filler.
4. The composition for curing resin according to any one of claims 1 to 3, wherein the curing agent (C) is at least 1 selected from imidazoles, aromatic amines, and polyfunctional phenols.
5. A cured product obtained by curing the composition for a curable resin according to any one of claims 1 to 4.
6. A semiconductor device comprising a semiconductor element in a cured product obtained by curing the composition for a curable resin according to any one of claims 1 to 4.
7. A method for producing a composition for curing a resin, comprising:
a step of mixing the following components to obtain a mixture,
(A) multifunctional benzoOxazine compounds, the multifunctional benzolsThe oxazine compound having at least two benzo groupsOxazine ring and is selected from multifunctional benzo having structural unit of formula (1)An oxazine compound and a multifunctional benzo represented by the structure of formula (2)At least 1 of the oxazine compounds,
(B) a polyfunctional epoxy compound having at least one norbornane structure and at least two epoxy groups,
(C) a curing agent for curing the epoxy resin composition,
(D) a cure accelerator which is a bisphenolate of a diazabicycloalkene;
processing the mixture into a powdery, spherical or granular composition for a cured resin;
in the formula (1), R represents a chain alkyl group having 1-12 carbon atoms, a cyclic alkyl group having 3-8 carbon atoms, or an aryl group having 6-14 carbon atoms, the aryl group may have a halogen or a chain alkyl group having 1-12 carbon atoms as a substituent, Z represents hydrogen, a hydrocarbon group having 1-8 carbon atoms and/or a linking group, each of which may be the same or different, and at least one is a linking group, benzoThe oxazine rings are linked to each other through the linking group;
in the formula (2), L is a 2-valent organic group having 1 to 5 aromatic rings or an alkylene group having 1 to 10 carbon atoms, and the organic group and the alkylene group may contain oxygen and/or sulfur.
8. The production method according to claim 7, wherein in the step of obtaining the mixture, (E) an inorganic filler is further mixed to obtain a mixture.
9. A method for producing a cured product, comprising a step of heating and curing the composition for a cured resin produced by the method according to claim 7 or 8 at 180 to 300 ℃.
Technical Field
The present invention relates to a composition for a curable resin for obtaining a cured product having high heat resistance, a cured product thereof, a composition for a curable resin, and a method for producing a cured product. Further, a semiconductor device using the cured product as an encapsulating material is provided.
Background
The cured resin is used for various applications such as semiconductor sealing materials and fiber-reinforced plastics. Heretofore, an epoxy resin, a phenol resin curing agent, and a curing accelerator have been used for a composition for curing a resin. In addition, as a curing accelerator generally used for curing an epoxy resin with a phenol resin, an organic phosphine compound and an imidazole compound are known.
However, the following problems are present in a composition for a curable resin comprising an epoxy resin and a phenol resin curing agent: when an organic phosphine compound is used, the reaction does not proceed sufficiently, and a cured product excellent in moldability, reliability at high temperatures, and crack resistance cannot be obtained; when an imidazole-based curing accelerator is used, the curing properties are excellent, but the fluidity and the storage stability of the resulting sealing resin composition are deteriorated.
In patent document 1, in order to solve the above-mentioned problems, it is proposed to use 1, 8-diazabicyclo (5.4.0) undecene-7 (DBU) as a curing accelerator in a composition for a cured resin comprising an epoxy resin and a phenol resin curing agent, from the viewpoint of improving curability, moldability and storage stability.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2004-203911
Disclosure of Invention
The present inventors have conducted a process for obtaining a curable resin composition having excellent fast curability and excellent heat resistance of a cured product thereof, the composition containing a benzo groupA composition for curing resins, which comprises an oxazine compound, a polyfunctional epoxy compound, a curing agent and a curing accelerator, has been developed.
In this connection, benzeneThe oxazine compound is meant to comprise a compound having a benzene skeleton andbenzo of oxazine skeletonOxazine ring compound, and benzo compound as cured product (polymer) thereofOxazine resins have excellent physical properties such as heat resistance and mechanical strength, and are used as high-performance materials in a wide variety of applications.
The present inventors have studied DBU as a compound containing benzoAs a result of the use of the curing accelerator for a curable resin composition comprising an oxazine compound and a polyfunctional epoxy compound, there have been found new problems aimed at stable production, such as the reaction initiation temperature being too low to control curing, and DBU being liquid at ordinary temperature to make it difficult to add an accurate amount of the curing accelerator to the production process.
Therefore, a composition for a cured resin which can be stably produced, has excellent fast curability, and a cured product thereof has excellent heat resistance is required.
The present inventors have conducted intensive studies to solve the above problems, and as a result, have developed a composition for a cured resin containing a polyfunctional benzo groupThe present inventors have found that the composition for a curable resin is excellent in rapid curability and that a cured product thereof is excellent in heat resistance, and have completed the present invention.
That is, according to the present invention, the following invention can be provided.
[1] A composition for curing a resin, comprising:
(A) multifunctional benzoOxazine compounds having at least two benzo groupsOxazine ring and is selected from multifunctional benzo having structural unit of formula (1)An oxazine compound and a multifunctional benzo represented by the structure of formula (2)At least 1 of the oxazine compounds,
(B) a polyfunctional epoxy compound having at least one norbornane structure and at least two epoxy groups;
(C) a curing agent;
(D) as curing accelerators for the bisphenolates of diazabicycloalkenes.
[ in the formula (1), R represents a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and the aryl group may have a halogen or a chain alkyl group having 1 to 12 carbon atoms as a substituent. Z represents hydrogen, a hydrocarbon group having 1 to 8 carbon atoms and/or a linking group, each of which may be the same or different, and at least one is a linking group, benzoThe oxazine rings are linked to each other via the linking group.]
In the formula (2), L is a 2-valent organic group having 1 to 5 aromatic rings or an alkylene group having 1 to 10 carbon atoms, and the organic group and the alkylene group may contain oxygen and/or sulfur. ]
[2] The composition for curing a resin according to [1], wherein the curing accelerator (D) is represented by the structure of formula (9) or (10).
[ in the formula (9), R represents an alkylene group which may have a substituent, a carbonyl group, a sulfonyl group or a thioether bond (-S-). ]
[ in the formula (10), R represents an alkylene group which may have a substituent, a carbonyl group, a sulfonyl group or a thioether bond (-S-). ]
[3] The composition for a curable resin according to [1] or [2], which further comprises (E) an inorganic filler.
[4] The composition for curing resin according to any one of [1] to [3], wherein the curing agent (C) is at least 1 selected from imidazoles, aromatic amines and polyfunctional phenols.
[5] A cured product obtained by curing the composition for a curable resin according to any one of [1] to [4 ].
[6] A semiconductor device comprising a semiconductor element provided in a cured product obtained by curing the composition for a curable resin according to any one of [1] to [4 ].
[7] A method for producing a composition for curing a resin, comprising:
a step of mixing the following components to obtain a mixture,
(A) multifunctional benzoOxazine compounds having two or more of benzoOxazine ring and is selected from multifunctional benzo having structural unit of formula (1)An oxazine compound and a multifunctional benzo represented by the structure of formula (2)At least 1 of the oxazine compounds,
(B) a polyfunctional epoxy compound having at least one norbornane structure and at least two epoxy groups,
(C) a curing agent for curing the epoxy resin composition,
(D) a curing accelerator which is a bisphenolate of a diazabicycloalkene;
and a step of processing the mixture into a powdery, spherical or granular composition for a cured resin.
[ in the formula (1), R represents a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and the aryl group may have a halogen or a chain alkyl group having 1 to 12 carbon atoms as a substituent. Z represents hydrogen, a hydrocarbon group having 1 to 8 carbon atoms and/or a linking group, each of which may be the same or different, and at least one is a linking group, benzoThe oxazine rings are linked to each other via the linking group.]
In the formula (2), L is a 2-valent organic group having 1 to 5 aromatic rings or an alkylene group having 1 to 10 carbon atoms, and the organic group and the alkylene group may contain oxygen and/or sulfur. ]
[8] The production method according to [7], wherein the step of obtaining the mixture further comprises mixing (E) an inorganic filler to obtain a mixture.
[9] A method for producing a cured product, comprising the step of heating and curing the composition for a curable resin produced by the method according to [7] or [8] at 180 to 300 ℃.
The curable resin composition of the present invention is a novel curable resin composition containing components (a) to (D) and, if necessary, component (E), and is characterized by: has excellent rapid curability, and a cured product thereof has a high glass transition temperature and excellent heat resistance. Therefore, the composition for a cured resin of the present invention can be used for applications requiring rapid curability and heat resistance, such as adhesives, sealants, coatings, matrix resins for composite materials, and the like. In particular, the sealing material for a semiconductor element can exhibit excellent sealing performance and contributes to high reliability of a semiconductor device.
Further, according to the method for producing a cured product of the present invention, a cured product having the above-described excellent performance and usable for the above-described applications can be formed in a short time.
Drawings
Fig. 1 is a graph showing a reaction start temperature and a reaction peak temperature in a measurement result of a typical Differential Scanning Calorimetry (DSC).
Detailed Description
[ composition for curing resin ]
The present invention will be described in detail below. The "compound" in the components (a) and (B) of the present invention includes not only the monomer shown in each formula but also an oligomer obtained by polymerizing a small amount of the monomer, that is, a prepolymer before forming a cured resin.
(component A)
The component (A) constituting the composition for a curable resin is a polyfunctional benzene selected from the group consisting of a polyfunctional benzene having a structural unit of the formula (1)An oxazine compound and a multifunctional benzo represented by the structure of formula (2)Having at least two benzo rings of at least 1 of the oxazine compoundsMultifunctional benzo of oxazine ringAn oxazine compound. Z in the formula (1) represents hydrogen, a substituent and/or a linking group (spacer), each of which may be the same or different, and at least one is a linking group, benzoThe oxazine rings are linked to each other via the linking group. It should be noted that the linking group here also includes two benzo groupsThe case where the oxazine ring is directly bonded without via other groups. Examples of the substituent include a hydrocarbon group having 1 to 8 carbon atoms.
Thus, more than two of the options for component (A) are benzoIn the compound in which the oxazine ring is bonded to the benzene ring moiety, the structural unit is represented by the above formula (1).
If a multifunctional benzo of the formula (1) is to be represented more specificallyThe oxazine compound may be represented by the structure shown in formula (1 a).
[ in the formula (1a), R represents a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and the aryl group may have a halogen or a chain alkyl group having 1 to 12 carbon atoms as a substituent. Each R may be the same or different. X is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, eachThey may be the same or different. Y is C1-6 alkylene, oxygen, sulfur, SO2A radical or a carbonyl group. m is 0 or 1. n is an integer of 1 to 10.]
Specific examples of R in the formulae (1) and (1a) include the following groups.
Examples of the chain alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.
Examples of the cyclic alkyl group having 3 to 8 carbon atoms include a cyclopentyl group and a cyclohexyl group.
Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenanthryl group and a biphenyl group.
The aryl group having 6 to 14 carbon atoms may be substituted, and examples of the substituent include a chain alkyl group having 1 to 12 carbon atoms and a halogen. Examples of the aryl group having 6 to 14 carbon atoms substituted with a chain alkyl group having 1 to 12 carbon atoms or a halogen include an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, an o-ethylphenyl group, an m-ethylphenyl group, a p-ethylphenyl group, an o-tert-butylphenyl group, a m-tert-butylphenyl group, a p-tert-butylphenyl group, an o-chlorophenyl group, and an o-bromophenyl group.
In view of good handling properties, R is preferably selected from the group consisting of methyl, ethyl, propyl, phenyl and p-tolyl.
Further, the component (A) may be a mixture of a plurality of compounds represented by the formula (1) or (1a) wherein R's are different from each other.
Examples of the hydrocarbyl group having 1 to 8 carbon atoms of the formulae (1) and (1a) include an alkyl group, an aryl group, and an aralkyl group, with an aryl group being preferred.
As a multifunctional benzo represented by formula (1) or (1a)Examples of the oxazine compound include a compound represented by the following formula (1X) and an oligomer obtained by polymerizing a small amount of the compound.
As a further option for component (A) polyfunctional benzols of the formula (2)The oxazine compound being two benzenesA compound in which nitrogen atoms (N atoms) of the oxazine ring are bonded to each other via a linking group L.
In the formula (2), L is a 2-valent organic group having 1 to 5 aromatic rings or an alkylene group having 1 to 10 carbon atoms, and the organic group and the alkylene group may contain oxygen and/or sulfur. ]
The composition of the present invention may contain a plurality of polyfunctional benzenes represented by formula (2) and differing in LAn oxazine compound as component (A).
When L in formula (2) is a group having an aromatic ring, the number of aromatic rings is 1 to 5, and examples thereof include monocyclic compounds, polycyclic compounds, and fused ring compounds. In addition, L may contain at least one selected from oxygen and sulfur.
Specific examples thereof include a group represented by the following formula (3).
When L in the formula (2) is an alkylene group, the number of carbon atoms is 1 to 10, preferably 1 to 6. Specific examples of the alkylene group include a methylene group, an ethylene group, an isopropylene group and the like, and a methylene group is preferable.
Multifunctional benzols as formula (2)Examples of the oxazine compound include a compound represented by the following formula (2X) and an oligomer obtained by polymerizing the compound, for example, an oligomer obtained by small-amount polymerization.
Multifunctional benzo as component (A)As the oxazine compound, commercially available ones can be used.
As a commercially available product, bisphenol F-aniline (F-a) type benzeneBenzoxazines, phenols-diaminodiphenylmethane (P-d) type benzenesOxazines (all manufactured by Sinationality Kabushiki Kaisha), and the like.
(component B)
The component (B) constituting the curable resin composition is a polyfunctional epoxy compound having at least one norbornane structure and at least two epoxy groups (hereinafter, also simply referred to as "polyfunctional epoxy compound"). The composition of the present invention may contain a variety of polyfunctional epoxy compounds as the component (B). The polyfunctional epoxy compound is preferably an alicyclic epoxy compound, and more preferably has an epoxy structure shown in the following formula (4) to which a 5-membered ring, a 6-membered ring or a norbornane ring is bonded.
Specific examples of the polyfunctional epoxy compound include compounds represented by the following formula (5).
An example of the production of the polyfunctional epoxy compound of the component (B) will be described.
The compound of the following formula (5-1) can be produced, for example, by synthesizing the following compound (a) having a norbornane structure by a diels-alder reaction of butadiene and dicyclopentadiene, and then reacting the compound (a) with m-chloroperoxybenzoic acid as shown in the following formula (6).
The compound of the following formula (5-2) can be produced, for example, by synthesizing the compound (b) having a norbornane structure (tricyclopentadiene) by diels-alder reaction of cyclopentadiene and dicyclopentadiene, and then reacting the compound (b) with m-chloroperoxybenzoic acid as shown in the following formula (7).
The compound of the following formula (5-3) can be produced, for example, by synthesizing the compound (c) having a norbornane structure by diels-alder reaction of butadiene and cyclopentadiene, and then reacting the compound (c) with m-chloroperoxybenzoic acid as shown in the following formula (8).
The compound of the following formula (5-4) can be produced, for example, by reacting dicyclopentadiene with potassium peroxymonosulfate (Oxone). The dicyclopentadiene diepoxide of the compound of formula (5-4) may be a commercially available product, and examples thereof include dicyclopentadiene diepoxide manufactured by SHANDONG QIHUAN biochemial co.
With respect to component (A) multifunctional benzoThe compounding ratio of the oxazine compound and the polyfunctional epoxy compound of the component (B) is preferably 5 parts by mass or more and 150 parts by mass or less, more preferably 10 parts by mass or more and 100 parts by mass or less, with respect to 100 parts by mass of the component (a). When the blending ratio of the components (A) and (B) is within this range, good heat resistance can be obtained.
The composition of the present invention contains a plurality of multifunctional benzenesWhen the oxazine compound is used as the component (a), the total amount of these compounds is defined as 100 parts by mass. When the composition of the present invention contains a plurality of polyfunctional epoxy compounds as the component (B), the above-mentioned "blending ratio of the component (B)" means a ratio of the total of these compounds.
(component C)
The component (C) constituting the composition for curing resin is a curing agent. The composition of the present invention preferably contains at least 1 curing agent selected from imidazoles, aromatic amines, polyfunctional phenols, and the like as the component (C). Examples of the component (C) include aromatic amines (e.g., diethyltoluenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylylenediamine, and derivatives thereof), aliphatic amines (e.g., triethylenetetramine, isophoronediamine, etc.), imidazoles (e.g., imidazole derivatives, etc.), dicyandiamide, tetramethylguanidine, carboxylic acid anhydrides (e.g., methylhexahydrophthalic anhydride, etc.), carboxylic acid hydrazides (e.g., adipic acid hydrazide, etc.), carboxylic acid amides, monofunctional phenols, polyfunctional phenols (e.g., bisphenol a, bisphenol F, bisphenol sulfides (e.g., bis (4-hydroxyphenyl) sulfide, etc.), polyphenol compounds, etc.), polythiols, carboxylic acid salts, lewis acid complexes (e.g., boron trifluoride ethylamine complex, etc.), and the like. These may be used alone or as a mixture of 2 or more.
The blending ratio of the component (C) is preferably in the range of 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, relative to 100 parts by mass of the total of the components (a) and (B). By containing the component (C) in this range, the curing reaction can be more efficiently performed, and a cured product having high heat resistance can be obtained.
(component D)
The component (D) constituting the composition for curing resin is a curing accelerator. The composition of the present invention uses a salt of a diazabicycloalkene with a bisphenol as component (D). Here, since DBU and the like are liquid at normal temperature, it is very difficult to add an accurate amount in the manufacturing process. However, since the bisphenol salt of the diazabicycloalkene is solid at normal temperature (20 ℃), the correct amount can be easily added to the composition for a cured resin in the production process, and stable production can be achieved. Further, by using a salt of a diazabicycloalkene and a bisphenol as the (D) curing accelerator, the compatibility of a melt obtained by melting the components (a), (B), and (C) with the (D) curing accelerator can be improved.
In addition, when a solvent is added at the time of producing the composition, by using a salt of diazabicycloalkene and bisphenol as the (D) curing accelerator, the compatibility of a dissolved product obtained by dissolving the components (a), (B), and (C) in the solvent and the (D) curing accelerator can be improved. The solvent is not particularly limited as long as it can dissolve components (a) to (C), and examples thereof include hydrocarbons, ethers, esters, and halogens.
Examples of the diazabicycloalkene used as component (D) include 1, 4-diazabicyclo (3.3.0) octene-4, 1, 5-diazabicyclo (4.2.0) octene-5, 3-methyl-1, 4-diazabicyclo (3.3.0) octene-4, 3,6,7, 7-tetramethyl-1, 4-diazabicyclo (3.3.0) octene-4, 1, 5-diazabicyclo (4.3.0) nonene-5, 1, 7-diazabicyclo (4.3.0) nonene-6, 1, 5-diazabicyclo (4.4.0) decene-5, 1, 8-diazabicyclo (5.3.0) decene-7, 9-methyl-1, 8-diazabicyclo (5.3.0) decene-7, 1, 8-diazabicyclo (5.4.0) undecene-7, 1, 8-diazabicyclo (5.3.0) undecene-7, 1, 8-diazabicyclo (7.2.0) undecene-8, 1, 6-diazabicyclo (5.5.0) dodecene-6, 1, 8-diazabicyclo (7.3.0) dodecene-8, 1, 10-diazabicyclo (7.3.0) dodecene-9, 1, 7-diazabicyclo (6.5.0) tridecene-7, 1, 8-diazabicyclo (7.4.0) tridecene-8, 1, 10-diazabicyclo (7.4.0) tridecene-9, 1, 8-diazabicyclo (7.5.0) tetradecene-8, 1, 14-diazabicyclo (11.3.0) hexadecene-13, and 1, 14-diazabicyclo (11.4.0) heptadecene-13, and the like. Of these diazabicycloalkenes, 1, 5-diazabicyclo (4.3.0) nonene-5 (DBN) and 1, 8-diazabicyclo (5.4.0) undecene-7 (DBU) are preferably used.
The bisphenol used as the component (D) is a compound having 2 hydroxyphenyl groups, and examples thereof include 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A), 1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP), 2-bis (4-hydroxyphenyl) hexafluoropropane (bisphenol AF), 2-bis (4-hydroxyphenyl) butane (bisphenol B), bis (4-hydroxyphenyl) diphenylmethane (bisphenol BP), 2-bis (3-methyl-4-hydroxyphenyl) propane (bisphenol C), bis (4-hydroxyphenyl) -2, 2-dichloroethylene (bisphenol C), 1-bis (4-hydroxyphenyl) ethane (bisphenol E), bis (4-hydroxyphenyl) methane (bisphenol F), 4,4' -Methylenediphenol (MDP), 2-bis (4-hydroxy-3-isopropylphenyl) propane (bisphenol G), 1, 3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene (bisphenol M), bis (4-hydroxyphenyl) sulfone (bisphenol S), 1, 4-bis (2- (4-hydroxyphenyl) -2-propyl) benzene (bisphenol P), 5' - (1-methylethylidene) -bis [1,1' - (biphenyl) -2-ol ] propane (bisphenol PH), 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane (bisphenol TMC), 1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), Bis (4-hydroxyphenyl) sulfide (TDP), and 4,4' -Dihydroxybenzophenone (DHBP).
As the bisphenol salt of the diazabicycloalkene as the component (D), a compound represented by the structure of formula (9) or formula (10) is preferable.
In the formulae (9) and (10), the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. Specific examples of the alkylene group include a methylene group, an ethylene group, an isopropylene group and the like, and a methylene group is preferable. The alkylene group may have 1 to 3 aromatic rings as substituents. Further, the alkylene group may contain at least 1 selected from oxygen, sulfur and halogen in the substituent. The halogen is preferably fluorine.
As the component (D), a bisphenolate of DBU or a bisphenolate of DBN is preferable, and specifically, a bisphenolate of DBU having a structure represented by the following formula (11) or a bisphenolate of DBN having a structure represented by the following formula (12) is more preferable. By using a bisphenolate of DBU or a bisphenolate of DBN as the component (D), the heat resistance of a cured product of the composition for curing a resin can be improved. Further, by using a bisphenolate of DBU or a bisphenolate of DBN as the component (D), the reaction initiation temperature of a cured product of the curable resin composition can be set to a preferred temperature.
The blending ratio of the component (D) is preferably in a range of 0.01 to 10 parts by mass relative to 100 parts by mass of the total of the components (a) and (B). More preferably, it is in the range of 0.1 to 7 parts by mass. By containing the component (D) in such a range, a cured resin composition having excellent rapid curability can be obtained.
(component E)
The curable resin composition of the present invention may further contain (E) an inorganic filler, if necessary.
For example, when the composition for a curable resin of the present invention is used for an application as a sealing material for a semiconductor device or the like, the component (E) is preferably contained. The inorganic filler used in the present invention is not particularly limited, and may be selected in consideration of the use of the composition or the cured product thereof, or the properties desired to be imparted. Hereinafter, this inorganic filler is referred to as component (E).
Examples of the component (E) include oxides such as silica, alumina, titania, zirconia, magnesia, ceria, yttria, calcium oxide, antimony trioxide, zinc oxide, and iron oxide; carbonates such as calcium carbonate, magnesium carbonate, barium carbonate, and strontium carbonate; sulfates such as barium sulfate, aluminum sulfate, and calcium sulfate; nitrides such as aluminum nitride, silicon nitride, titanium nitride, boron nitride, and manganese nitride; silicon compounds such as calcium silicate, magnesium silicate and aluminum silicate; boron compounds such as aluminum borate; zirconium compounds such as barium zirconate and calcium zirconate; phosphorus compounds such as zirconium phosphate and magnesium phosphate; titanium compounds such as strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, barium titanate, and potassium titanate; minerals such as mica, talc, kaolin clay, kaolinite, halloysite, cordierite, pyrophyllite, montmorillonite, sericite, bauxite, bentonite, asbestos, wollastonite, sepiolite, xonotlite, zeolite, hydrotalcite, hydrated gypsum, alum, diatomaceous earth, and boehmite; fly ash, dehydrated sludge, glass beads, glass fibers, silica sand, basic magnesium sulfate, silicon oxide, silicon carbide and the like; metals such as copper, iron, cobalt, nickel, or alloys containing any of them; magnetic materials such as ferrosilicon-aluminum alloy, alnico magnet, ferrite, and the like; graphite, coke, and the like. Component (E) is preferably silica or alumina. Examples of the silica include fused silica, spherical silica, crystalline silica, amorphous silica, synthetic silica, hollow silica and the like, and among them, spherical silica and crystalline silica are preferable. The component (E) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The component (E) may be in the form of particles, and the average particle diameter in this case is not particularly limited, and may be, for example, 0.01 to 150 μm, preferably 0.1 to 120 μm, and more preferably 0.5 to 75 μm. If the amount is within this range, for example, when the composition of the present invention is used for sealing materials for semiconductor devices, the filling property in the cavity of a mold will be good. The average particle diameter of the component (E) can be measured by a laser diffraction/scattering method. Specifically, the measurement can be performed in the following manner: the particle size distribution of the inorganic filler was prepared on a volume basis using a laser diffraction particle size distribution measuring apparatus, and the median particle size was defined as the average particle size. The measurement sample may be one obtained by dispersing an inorganic filler in water by ultrasonic waves. As the laser diffraction type particle size distribution measuring apparatus, "LA-500", "LA-750", "LA-950", "LA-960" and the like available from horiba, Ltd.
The blending ratio of the component (E) is not particularly limited as long as a cured product having high heat resistance can be obtained, and may be appropriately set according to the application. For example, when the composition is used for semiconductor sealing applications, the following compounding ratios are preferred.
The lower limit of the blending ratio of the component (E) may be, for example, 150 parts by mass or more, preferably 400 parts by mass or more, and more preferably 500 parts by mass or more, to 100 parts by mass of the total of the components (a), (B), (C), and (D). The upper limit of the blending ratio of the component (E) is 1300 parts by mass or less, preferably 1150 parts by mass or less, and more preferably 950 parts by mass or less. When the lower limit of the blending ratio of the component (E) is 400 parts by mass or more, increase in moisture absorption amount and decrease in strength accompanying curing of the curable resin composition can be suppressed, and therefore, a cured product having good solder crack resistance can be obtained. Further, if the upper limit of the blending ratio of the component (E) is 1300 parts by mass or less, the composition for a curable resin has fluidity and is easily filled into a mold, and a cured product exhibits good sealing performance.
(other Components)
The composition of the present invention may contain a benzo group other than the component (A) within a range not impairing the effects of the present inventionAn oxazine compound. For example, where it is desired to reduce the viscosity of the composition, the benzene may be substitutedMonofunctional benzenes having 1 oxazine ringAn oxazine compound is added to the composition.
The composition for a curable resin of the present invention may contain, for example, nanocarbon, a flame retardant, a mold release agent, and the like, within a range not impairing the performance thereof.
Examples of the nanocarbon include a carbon nanotube, a fullerene, and derivatives thereof.
Examples of the flame retardant include phosphoric acid esters and boric acid esters such as red phosphorus, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, xylyldiphenyl phosphate, resorcinol bisphenyl phosphate, and bisphenol a bis (diphenyl phosphate).
Examples of the release agent include silicone oil, stearate, carnauba wax, and the like.
When the composition for a curable resin of the present invention is used for semiconductor sealing applications, colorants such as carbon black, iron oxide, and titanium oxide may be appropriately added in addition to the components (a) to (E) within a range that does not impair the performance of the composition for a curable resin; natural waxes such as carnauba wax, synthetic waxes such as oxidized polyethylene wax, higher fatty acids such as stearic acid, metal salts such as zinc stearate, and mold release agents such as paraffin wax; low stress additives such as silicone oil and silicone rubber; and 1 or more of metal hydroxides such as calcium hydroxide, aluminum hydroxide, and magnesium hydroxide, and flame retardants such as phosphazene.
The blending ratio of the other component is preferably in the range of 0.01 to 15 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, relative to 100 parts by mass of the total of the components (a) and (B).
[ method for producing composition for curing resin ]
Next, a method for producing the curable resin composition of the present invention will be described.
The curable resin composition of the present invention can be produced by mixing the components (a) to (D), and if necessary, the component (E) and other components such as other additives, and a solvent with a kneading or mixing apparatus.
The kneading or mixing method is not particularly limited, and mixing can be performed using, for example, a planetary mixer, a twin-screw extruder, a mixer such as a hot roll or a kneader, or the like. When the components (a) and (B) are in a liquid or solid state having high viscosity at room temperature, or when the component (E) is contained, they may be kneaded by heating as necessary, or may be further kneaded under a pressurized or reduced pressure condition. The heating temperature is preferably 80 to 120 ℃.
Since the composition for a curable resin containing the component (E) is solid at room temperature, it may be heated and kneaded, then cooled and pulverized to prepare a powder, or the powder may be tableted to prepare pellets. Further, the powder may be granulated to prepare a granular form.
When the curable resin composition of the present invention does not contain the component (E) and is used for a prepreg for FRP, the curable resin composition preferably has a viscosity of 10 to 3000Pa · s at 50 ℃. More preferably 10 to 2500 pas, and still more preferably 100 to 2000 pas. When the composition is used for sealing materials or coating applications, the viscosity is not particularly limited as long as the composition does not interfere with operations such as sealing and coating.
(Properties of composition for curing resin)
The curing performance of the composition for a curable resin of the present invention can be measured as thermophysical properties (reaction initiation temperature and reaction peak temperature) by Differential Scanning Calorimetry (DSC). Specifically, the measurement can be carried out at a temperature range of 30 ℃ to 300 ℃ at a temperature rise rate of 10 ℃/min using a differential scanning calorimeter. The temperature at which the graph begins to rise at 100 ℃ or higher was taken as the reaction start temperature, and the highest point in the graph was taken as the reaction peak temperature. In order to prevent unnecessary reactions that proceed at low temperatures, the reaction start temperature is preferably 110 ℃ or higher, more preferably 120 ℃ or higher, still more preferably 130 ℃ or higher, and furthermore preferably 190 ℃ or lower, more preferably 180 ℃ or lower. From the viewpoint of reactivity, the reaction peak temperature is preferably 195 ℃ or more, more preferably 200 ℃ or more, and further preferably 230 ℃ or less, more preferably 220 ℃ or less, and further preferably 215 ℃ or less.
The curing performance of the composition for a cured resin of the present invention can be measured as a gel time. From the viewpoint of rapid curability, the gel time of the curable resin composition measured at 200 ℃ is preferably 10 to 60 seconds, and more preferably 20 to 55 seconds. The gel time can be measured according to the gel time B method (flat plate method) of JIS K6910 (2007).
[ cured product ]
The cured product of the composition for a curable resin of the present invention has characteristics of good heat resistance, difficulty in thermal decomposition, and high glass transition temperature. The reason why the composition for a curable resin of the present invention forms such an excellent cured product is considered to be the following reason.
First, in benzeneIn homopolymerization of oxazines, phenolic hydroxyl groups are formed by polymerization. It is considered that the phenolic hydroxyl group undergoes keto-enol tautomer at a high temperature, for example, 200 ℃ or higher, whereby the polymer chain is cleaved, and therefore, the heat resistance is low and the glass transition temperature is also lowered.
On the other hand, the polyfunctional epoxy compound having a norbornane structure and two or more epoxy groups of the present invention is difficult to homopolymerize, and it is considered that the polyfunctional epoxy compound is derived from the above-mentioned benzo groupPhenolic hydroxyl groups of the oxazine react to prevent the cleavage of the polymer chains. Therefore, a cured product having high heat resistance can be obtained.
(Properties of cured product)
The heat resistance of the cured product of the present invention can be evaluated by measuring the glass transition temperature. The glass transition temperature is preferably 240 ℃ or higher, more preferably 250 ℃ or higher. The glass transition temperature can be measured by Differential Scanning Calorimetry (DSC). Such measurement can be easily carried out by using a commercially available differential scanning calorimeter (for example, manufactured by Hitachi High-Tech Science Company).
[ method for producing cured product ]
The cured product of the present invention can be obtained by reacting the cured product with a known benzeneAnd (b) a ring-opening polymerization and curing under the same curing conditions as the oxazine compound and/or the epoxy compound. For example, the following methods can be mentioned.
First, the curable resin composition of the present invention is produced by the above method. Then, the obtained composition for a cured resin is heated at 180 to 300 ℃ for 1 minute to 1 hour or 1 minute to 5 hours, whereby a cured product can be obtained. In view of continuous production of the cured product, a curing time of 1 to 3 minutes or 1 to 6 minutes is sufficient, but in view of obtaining higher strength, it is preferable to further heat the cured product for about 5 minutes to 1 hour or about 5 minutes to 5 hours.
Further, a benzo group other than the component (A) may be blended within a range not impairing the effects of the present inventionAn oxazine compound and/or an epoxy compound other than the component (B) to obtain a cured product.
When a film-shaped product is obtained as a cured product, a composition having a solution viscosity suitable for forming a thin film may be prepared by further mixing a solvent. The solvent is not particularly limited as long as it can dissolve components (a) to (E), and examples thereof include hydrocarbons, ethers, esters, and halogen-containing compounds.
In the case where the curable resin composition is dissolved in the solvent in such a manner to obtain a solution, the solution-form curable resin composition may be applied to a substrate or the like, and then the solvent may be volatilized and then cured by heat to obtain a cured product.
[ semiconductor device ]
The semiconductor device of the present invention is a semiconductor device provided with a semiconductor element in a cured product obtained by curing the curable resin composition of the present invention containing the components (a) to (D) and, if necessary, (E). Here, the semiconductor element is generally supported and fixed by a lead frame which is a thin plate of a metal material. The phrase "a semiconductor element is provided in a cured product" means that the semiconductor element is encapsulated by a cured product of the curable resin composition, and indicates a state in which the semiconductor element is covered with the cured product. In this case, the entire semiconductor element may be covered, or the surface of the semiconductor element provided on the substrate may be covered.
When various electronic components such as a semiconductor element are sealed with the cured product of the present invention to manufacture a semiconductor device, the sealing step can be performed by a conventional molding method such as transfer molding, compression molding, or injection molding to manufacture the semiconductor device.
Examples
The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
<Component (A): multifunctional benzoOxazine compounds>
The following (a1) to (a2) were used as the component (a).
(A1) The method comprises the following steps A phenol-diaminodiphenylmethane (P-d) type benzo represented by the following formula (2-1)Oxazine (made by four kingdoms Kabushiki Kaisha)
(A2) (ii) a A bisphenol F-aniline (F-a) -type benzo represented by the following formula (1-1)Oxazine (made by four kingdoms Kabushiki Kaisha)
< ingredient (B): alicyclic epoxy Compound >
The following (B1) to (B3) were used as the component (B).
(B1) Alicyclic epoxy compound 1: a compound of the formula (5-1)
The compound (a) represented by the above formula (6) was synthesized according to the method described in "Diels-Alder reaction of butadiene and cyclopentadiene-determination of trimer-", J.P.O., J.Ohio, 1972, Vol.15, No. 3, p189-192 ".
Next, the reaction of the above formula (6) is carried out in the following manner. 23.5kg of chloroform and 1.6kg of the compound (a) were charged into a reaction vessel, and 4.5kg of m-chloroperoxybenzoic acid was added dropwise thereto at 0 ℃ with stirring. The reaction mixture was warmed to room temperature and reacted for 12 hours.
Subsequently, m-chlorobenzoic acid formed as a by-product was removed by filtration, and the filtrate was washed with 1N aqueous sodium hydroxide solution 3 times and then with saturated brine. The organic layer was dried over magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated to give a crude product.
2kg of toluene was added to the crude product, and the mixture was dissolved at room temperature. 6kg of heptane was added dropwise thereto to conduct crystallization, followed by aging at 5 ℃ for 1 hour. The crystalline precipitate was filtered off and washed with hexane. Drying was carried out at 35 ℃ for 24 hours under reduced pressure, whereby 1.4kg of a compound represented by the following formula (5-1) was obtained as a white solid.
(B2) Alicyclic epoxy compound 2: a compound of the formula (5-2) (tricyclopentadiene diepoxide)
Compound (b) was synthesized in the same manner as compound (a) according to the method described in the above-mentioned document.
Next, the reaction of the above formula (7) is carried out in the following manner. 59.2kg of chloroform and 4.0kg of the compound (b) were charged into a reaction vessel, and 10.6kg of m-chloroperoxybenzoic acid was added dropwise thereto at-10 ℃ with stirring. The reaction mixture was warmed to room temperature and reacted for 12 hours.
Subsequently, m-chlorobenzoic acid formed as a by-product was removed by filtration, and the filtrate was washed with 42.0kg of a 5% aqueous sodium sulfite solution. The organic layer was washed 4 times with 41.6kg of a 1N aqueous solution of sodium hydroxide and then with 48.0kg of a saturated saline solution. The organic layer was dried over magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated to obtain 5.1kg of a crude product.
To the crude product was added 3.5kg of toluene, and the mixture was dissolved at room temperature. 13.7kg of heptane was added dropwise thereto to conduct crystallization, followed by aging at 5 ℃ for 1 hour. The crystalline precipitate was collected by filtration and washed with heptane. Drying was carried out at 35 ℃ for 12 hours under reduced pressure, whereby 2.8kg of a compound represented by the following formula (5-2) was obtained as a white solid.
(B3) Alicyclic epoxy compound 3: a compound of the formula (5-4) (dicyclopentadiene diepoxide)
10kg of dicyclopentadiene, 68kg of sodium bicarbonate, 100L of acetone and 130L of ion-exchanged water were put into a reaction vessel, and after cooling to 10 ℃ or lower, the reaction solution was controlled to be cooled so that the temperature of the reaction solution was maintained at 30 ℃ or lower, and 84kg of potassium peroxymonosulfate was slowly added thereto and the reaction was carried out for 10 hours while stirring.
Next, the reaction product was extracted 2 times with ethyl acetate 100L, and the resulting organic layers were separated and combined. Subsequently, the organic layer was washed with 100L of a mixed aqueous solution of sodium chloride and sodium thiosulfate (20 wt% of sodium chloride + 20 wt% of sodium thiosulfate), and then further washed with 100L of ion-exchanged water 2 times.
The washed organic layer was dried over magnesium sulfate, the magnesium sulfate was removed by filtration, and the organic solvent was distilled off from the filtrate to obtain 11kg of a compound represented by the following formula (5-4) as a white solid.
< ingredient (C): curing agent >
The following (C1) to (C2) were used as the component (C).
(C1) The method comprises the following steps Bis (4-hydroxyphenyl) sulfide (TDP) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) represented by the following formula
(C2) The method comprises the following steps Bis (4-hydroxyphenyl) methane (bisphenol F) (product of Kyowa chemical Co., Ltd.) represented by the following formula
< ingredient (D): curing accelerators >
The following (D1) to (D14) were used as the component (D).
(D1) The method comprises the following steps Salt represented by the following formula (TPP-K) (manufactured by Beixing chemical industry Co., Ltd.)
(D2) The method comprises the following steps A compound (DBU) (manufactured by San-Apro Ltd.) represented by the following formula
(D3) The method comprises the following steps A compound (DBN) (manufactured by San-Apro Ltd.)
(D4) The method comprises the following steps Curing accelerator U-CATSA102 for epoxy (Novolac varnish resin salt of DBU, San-Apro Ltd.)
(D5) The method comprises the following steps The curing accelerators used in examples 1 to 5 and 16 to 19 were prepared in the following manner. DBU (San-Apro Ltd.) and 4,4' -Methylenediphenol (MDP) (Tokyo chemical Co., Ltd.) were weighed in a 200ml round-bottomed flask with a cooling tube at a molar ratio of 1:1, placed in a stirrer, and heated in an oil bath at 100 ℃ with stirring, to obtain a pink crystalline salt. The structural formula of the obtained salt is shown as follows.
(D6) The method comprises the following steps The curing accelerators used in examples 6 to 7 and 20 to 21 were prepared by the same procedure as in (D5). DBU (manufactured by San-Apro Ltd.) and bisphenol F (manufactured by chemical industries, Japan) were heated while being stirred, and as a result, a salt of pale pink crystals was obtained. The structural formula of the obtained salt is shown as follows.
(D7) The method comprises the following steps The curing accelerators used in examples 8 and 22 were prepared by the same procedure as in (D5). DBU (manufactured by San-Apro Ltd.) and bis (4-hydroxyphenyl) sulfide (manufactured by Tokyo chemical Co., Ltd.) were heated while stirring, and as a result, white crystals of the salt were obtained. The structural formula of the obtained salt is shown as follows.
(D8) The method comprises the following steps The curing accelerator used in example 9 was prepared by the same procedure as in (D5). DBU (manufactured by San-Apro Ltd.) and 4,4' -dihydroxybenzophenone (manufactured by Tokyo chemical Co., Ltd.) were heated while stirring, and as a result, a yellow crystalline salt was obtained. The structural formula of the obtained salt is shown as follows.
(D9) The method comprises the following steps The curing accelerator used in example 10 was prepared by the same procedure as in (D5). DBU (manufactured by San-Apro Ltd.) and bisphenol AF (manufactured by Tokyo chemical industry Co., Ltd.) were heated while being stirred, and as a result, a salt having light brown crystals was obtained. The structural formula of the obtained salt is shown as follows.
(D10) The method comprises the following steps The curing accelerator used in example 11 was prepared by the same procedure as in (D5). DBU (manufactured by San-Apro Ltd.) and bisphenol AP (manufactured by Tokyo chemical industry Co., Ltd.) were heated while being stirred, and as a result, a gray crystalline salt was obtained. The structural formula of the obtained salt is shown as follows.
(D11) The method comprises the following steps The curing accelerator used in example 12 was prepared by the same procedure as in (D5). DBU (manufactured by San-Apro Ltd.) and bisphenol BP (manufactured by Tokyo chemical industry Co., Ltd.) were heated while being stirred, and as a result, white crystalline salt was obtained. The structural formula of the obtained salt is shown as follows.
(D12) The method comprises the following steps The curing accelerator used in example 13 was prepared by the same procedure as in (D5). DBN (manufactured by San-Apro Ltd.) and 4,4' -methylenediphenol (manufactured by Tokyo chemical Co., Ltd.) were heated while stirring, and as a result, a salt of light pink crystals was obtained. The structural formula of the obtained salt is shown as follows.
(D13) The method comprises the following steps The curing accelerator used in example 14 was prepared by the same procedure as in (D5). DBN (manufactured by San-Apro Ltd.) and bisphenol F (manufactured by Kyoto chemical Co., Ltd.) were heated while stirring, and as a result, white crystalline salt was obtained. The structural formula of the obtained salt is shown as follows.
(D14) The method comprises the following steps The curing accelerator used in example 15 was prepared by the same procedure as in (D5). DBN (San-Apro Ltd.) and bis (4-hydroxyphenyl) sulfide (product of chemical industries, Japan) were heated while stirring, and as a result, white crystals of the salt were obtained. The structural formula of the obtained salt is shown as follows.
< ingredient (E): inorganic Filler >
As component (E), fused spherical silica (FB-820, manufactured by DENKA K.K.) having an average particle diameter D50 of 22 μm was used. Hereinafter referred to as (E).
< other ingredients >
As the release agent, carnauba wax (manufactured by Clariant Japan) was used, and as the colorant, carbon black (MA600, manufactured by mitsubishi chemical corporation) was used.
(example 1)
A composition for a cured resin (hereinafter, simply referred to as "composition") and a cured product were prepared as described below, and the thermophysical properties (reaction start temperature and reaction peak temperature) of Differential Scanning Calorimetry (DSC) as an evaluation of curability and the glass transition temperature as an evaluation of heat resistance were measured.
The components (a1), (B1), (C1) and (D5) were kneaded at the compounding ratios shown in table 1 on a hot plate with a surface temperature of 100 ℃ for 10 minutes under atmospheric pressure, and then cooled to room temperature to obtain a mixture. The mixture was pulverized into powder with a mortar to obtain a composition.
< thermal Properties of Differential Scanning Calorimetry (DSC) >
The measurement was carried out by placing 10mg of the composition in an aluminum dish under a nitrogen flow at a temperature rising rate of 10 ℃/min in a temperature range from 30 ℃ to 300 ℃ using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Company: DSC 7020). The temperature at which the graph begins to rise at 100 ℃ or higher was taken as the reaction start temperature, and the highest point in the graph was taken as the reaction peak temperature. If the reaction start temperature is too low, the reaction may proceed at a low temperature and the reactivity may be too high. On the other hand, if the reaction start temperature is too high, the reaction may not proceed sufficiently, resulting in poor reactivity. Further, if the reaction start temperature is too high, the gel time (i.e., curing time) at the time of curing becomes too long, i.e., rapid curability may deteriorate. From the viewpoint of control in the production process, the difference between the reaction start temperature and the reaction peak temperature is preferably small. The results are shown in Table 1. Fig. 1 shows a reaction start temperature and a reaction peak temperature in a typical measurement result (an example) of DSC.
< glass transition temperature: tg >
About 10mg of the composition was weighed out into an aluminum dish used in DSC, and heated in an oven at 220 ℃ for 4 hours to obtain a cured product. The Tg of the resulting cured product was measured by DSC under the following conditions. The results are shown in Table 1.
The device comprises the following steps: X-DSC-7000 (manufactured by Hitachi High-Tech Science Company)
The measurement conditions were as follows: n is a radical of2Flow rate: 20 mL/min, rate of temperature rise: 20 ℃ per minute
< compatibility >
The resin melts were obtained by weighing (a1), (B1) and (C1) at the compounding ratios shown in table 1, melting at 200 ℃, adding (D5) the curing accelerator at the compounding ratio shown in table 1 to the resin melt, and visually evaluating whether or not the curing accelerator was compatible with each other according to the following criteria. The compatibility is confirmed by an evaluator with good vision (vision of 0.7 or more) under light of 300 to 2000 lux of illuminance. Confirmation was performed by 3 evaluators.
[ evaluation standards ]
O ·: the curing accelerator is compatible with the resin.
X: the curing accelerator is not compatible with the resin or is not sufficiently compatible with the resin.
If the compatibility is poor, the curing accelerator may be separated from the other composition, and the reaction may not proceed sufficiently and uniformly, and the product properties may vary, which is not preferable.
(examples 2 to 15)
Compositions of examples were prepared in the same manner as in example 1 except that the blending ratio of each component was as shown in table 1. The thermal properties (reaction start temperature and reaction peak temperature), heat resistance (glass transition temperature) and compatibility of the DSC were measured for each composition in the same manner as in example 1. The results are shown in Table 1.
Comparative examples 1 to 5
Compositions of comparative examples were prepared in the same manner as in example 1, except that the blending ratio of each component was as shown in table 1. The thermal properties (reaction start temperature and reaction peak temperature), heat resistance (glass transition temperature) and compatibility of the DSC were measured for each composition in the same manner as in example 1. The results are shown in Table 1. Among them, the cured resin compositions of comparative examples 3 and 4 started to cure at a kneading stage, that is, at a temperature of 100 ℃ or less, and therefore, the reaction start temperature and the reaction peak temperature by a differential scanning calorimeter could not be measured.
[ Table 1]
(example 16)
A composition for a cured resin (hereinafter, simply referred to as "composition") and a cured product were prepared as described below, and the gel time as an evaluation of curability and the glass transition temperature as an evaluation of heat resistance were measured.
The components (A1), (B1), (C1), (D5), (E), carnauba wax and carbon black were kneaded at the compounding ratio shown in Table 2 under atmospheric pressure for 10 minutes using a hot roll kneader (BR-150HCV, AIMEX) having 2 rolls with surface temperatures of 90 ℃ and 100 ℃ and then cooled to room temperature to obtain a mixture. The mixture was pulverized into a powder by Mini Speed Mill MS-09 (manufactured by Labonect) so as to be satisfactorily filled into a mold, thereby obtaining a composition.
< gel time >
According to the gelation time B method (flat plate method) of JIS K6910(2007), the composition was placed on a hot plate controlled at 200 ℃, stirred using a spatula, and a thermosetting reaction was performed until stirring became impossible, and the time (seconds) until fluidity was lost was measured as the gel time. The smaller the value of the gel time, the faster the curing rate, and the more excellent the quick curability. The results are shown in Table 2.
< glass transition temperature: tg >
The prepared composition was cured by a transfer molding machine under conditions of a mold temperature of 200 ℃, an injection pressure of 4MPa and a curing time of 3 minutes, and further heated in an oven at 240 ℃ for 4 hours as a post-curing treatment to obtain a cured product having a length of 3mm in the longitudinal direction by 3mm in the transverse direction by 15mm in the length direction. The Tg was measured by DSC under the following conditions using a test piece obtained by cutting the cured product into pieces each having a size of 3mm in length by 3mm in width by 2mm in length. The results are shown in Table 2.
The device comprises the following steps: X-DSC-7000 (manufactured by Hitachi High-Tech Science Company)
The measurement conditions were as follows: n is a radical of2Flow rate: 20 mL/min, rate of temperature rise: 20 ℃ per minute
(examples 17 to 22)
Compositions of examples were prepared in the same manner as in example 16, except that the blending ratio of each component was changed as shown in table 2. The gel time and heat resistance (glass transition temperature) of each composition were measured in the same manner as in example 16. The results are shown in Table 2.
Comparative examples 6 to 7
Compositions of comparative examples were prepared in the same manner as in example 16, except that the blending ratio of each component was as shown in table 2. The gel time and heat resistance (glass transition temperature) of each composition were measured in the same manner as in example 16. The results are shown in Table 2.
[ Table 2]