Resin molding materials

Abstract

To provide a resin molding material with excellent tracking resistance, heat resistance, and moldability. [Solution] The resin molding material of the present invention contains a diallyl phthalate resin, and is characterized in that the comparative tracking index according to (Method 1) below is 800V or higher, and the glass transition temperature is 200°C or higher and 300°C or lower. (Method 1) A resin molding material is transfer molded under the conditions of a mold temperature of 165°C, an injection pressure of 5MPa, and a curing time of 240 seconds to obtain a circular molded body with a diameter of 50mm and a thickness of 3mm. The comparative tracking index of the obtained molded body is then measured. At voltages of 600V or less, the measurement is performed in accordance with the test method specified in the international standard IEC60112. At voltages exceeding 600V, the electrode is fixed in accordance with the test method specified in the international standard IEC60112 by rotating it 180° with the longitudinal direction of the electrode as the axis of rotation, so that the angle between the molded body and the electrode is 30°.

Description

Technical Field

[0001] The present invention relates to a resin molding material.

Background Art

[0002] Molding materials using diallyl phthalate resins are used in electrical and electronic components such as coil bobbins, switch cases, terminal boards, connectors, magnet switches, and insulating sheets because they are excellent in electrical properties, dimensional stability, and water resistance, and various developments have been made so far.

[0003] For example, Patent Document 1 discloses a resin molding material that provides solder heat resistance by having a basic composition of 100 parts by mass of a diallyl isophthalate resin, 130 to 200 parts by mass of glass fiber, and 0.2 to 2.0 parts by mass of a curing catalyst.

[0004] In recent years, for example, in applications such as electric vehicles, as the voltage and current are increasing, materials with high tracking resistance (CTI) and high heat resistance are required, but achieving both has been difficult until now.

[0005] The reasons why it is difficult to achieve both tracking resistance and heat resistance are considered as follows. That is, for example, many resins with high heat resistance have a rigid structure with aromatic rings, but these resins are estimated to have a high char residue rate and work unfavorably on tracking resistance.

[0006] If a material has high tracking resistance, the creepage distance in electronic components can be reduced, so that the components can be miniaturized. Furthermore, if a material has high heat resistance, its reliability in a high-temperature environment is high.

[0007] Thus, a resin molding material that achieves both tracking resistance and heat resistance is required, but until now, a sufficient one has not been obtained. In addition, excellent moldability is also required in resin molding materials.

Prior Art Documents

[0008] [Patent Document 1] Patent No. 3045211 [Overview of the project] [Problems that the invention aims to solve]

[0009] The object of the present invention is to provide a resin molding material that has excellent tracking resistance, heat resistance, and moldability. [Means for solving the problem]

[0010] These objectives are achieved by the present invention as described in (1) to (5) below. (1) A resin molding material containing diallyl phthalate resin, The comparative tracking index CTI obtained by (Method 1) below is 800V or higher, A resin molding material characterized by having a glass transition temperature (Tg) of 200°C or higher and 300°C or lower. (Method 1) Under the conditions of a mold temperature of 165°C, an injection pressure of 5MPa, and a curing time of 240 seconds, a resin molding material is transfer-molded to obtain a circular molded body with a diameter of 50mm and a thickness of 3mm, and the comparative tracking index is measured for the obtained molded body. At this time, for voltages of 600V or less, the measurement is performed in accordance with the test method specified in the international standard IEC60112, and for voltages exceeding 600V, the electrode in the test method specified in the international standard IEC60112 is rotated 180° with the longitudinal direction of the electrode as the axis of rotation, and the electrode is fixed so that the angle between the molded body and the electrode becomes 30°, and the measurement is performed.

[0011] (2) The resin molding material described in (1) above, further comprising a diallyl phthalate compound in a non-polymerized state.

[0012] (3) The resin molding material according to (2) above, wherein the non-polymerized diallyl phthalate compound is diallyl isophthalate.

[0013] (4) Further containing aluminum hydroxide, When the total content rate [% by mass] of the diallyl phthalate resin and the non-polymerized diallyl phthalate compound is x, and the content rate [% by mass] of the aluminum hydroxide is y, The resin molding material according to (2) or (3) above, which satisfies the condition of y > 1.07x - 27.6 (where 20 ≤ x ≤ 45).

[0014] (5) The resin molding material according to any one of (1) to (4) above, wherein the diallyl phthalate resin is a diallyl isophthalate resin. [Advantages of the Invention]

[0015] According to the present invention, a resin molding material excellent in tracking resistance, heat resistance, and moldability can be provided. [Brief Description of the Drawings]

[0016] [Figure 1] It is a graph showing the total content rate (total blending amount) of the diallyl phthalate resin and the non-polymerized diallyl phthalate compound on the horizontal axis (x-axis) and the content rate (blending amount) of aluminum hydroxide on the vertical axis (y-axis) for the resin molding material. [Figure 2] It is a graph showing the total content rate (total blending amount) of the diallyl phthalate resin and the non-polymerized diallyl phthalate compound on the horizontal axis (x-axis) and the content rate (blending amount) of aluminum hydroxide on the vertical axis (y-axis) for the resin molding materials of each example and each comparative example. [Embodiments for Carrying Out the Invention]

[0017] Hereinafter, preferred embodiments of the present invention will be described in detail. [1] Resin molding material The resin molding material of the present invention will be described.

[0018] The resin molding material of the present invention is a resin molding material containing a diallyl phthalate resin, and is characterized in that the comparative tracking index CTI by the following (Method 1) is 800 V or more, and the glass transition temperature Tg is 200 °C or more and 300 °C or less. (Method 1) Under the conditions of a mold temperature of 165 °C, an injection pressure of 5 MPa, and a curing time of 240 seconds, the resin molding material is transfer molded to obtain a circular molded body with a diameter of 50 mm and a thickness of 3 mm, and the comparative tracking index is measured for the obtained molded body. At this time, when the voltage is 600 V or less, the measurement is performed according to the test method defined in the international standard IEC60112, and when the voltage exceeds 600 V, the electrodes in the test method defined in the international standard IEC60112 are rotated 180° with the longitudinal direction of the electrodes as the axis of rotation, and the measurement is performed by fixing the electrodes so that the angle between the molded body and the electrodes becomes 30°.

[0019] With such a configuration, it is possible to provide a resin molding material excellent in tracking resistance, heat resistance, and moldability.

[0020] Such an effect is obtained because the comparative tracking index CTI is 800 V or more, so that the tracking resistance can be made excellent, and because the glass transition temperature Tg is 200 °C or more and 300 °C or less, the heat resistance and moldability can be made excellent.

[0021] Also, for example, the insulation property under high temperature and high humidity can be made particularly excellent. Therefore, the resin molding material of the present invention can be suitably used, for example, as a sealing material for sealing semiconductor elements, substrates, terminals, coils, magnets, etc.

[0022] The excellent effect according to the present invention is obtained because the resin molding material has the above-described configuration, and cannot be obtained when it does not have the above-described configuration.

[0023] For example, when the comparative tracking index CTI is less than the above lower limit value, the tracking resistance cannot be made sufficiently excellent.

[0024] Furthermore, if the glass transition temperature Tg is below the aforementioned lower limit, sufficient heat resistance cannot be obtained. On the other hand, if the glass transition temperature Tg exceeds the aforementioned upper limit, the moldability will decrease.

[0025] The comparative tracking index (CTI) should be 800V or higher, but preferably 850V or higher, and more preferably 900V or higher. This makes the effects of the present invention described above even more pronounced.

[0026] Furthermore, the upper limit of the comparative tracking index CTI may be set to 1200V or less, or to 1000V or less.

[0027] The glass transition temperature Tg of the resin molding material of the present invention may be 200°C or more and 300°C or less, but is preferably 210°C or more and 290°C or less, more preferably 220°C or more and 280°C or less, and even more preferably 230°C or more and 270°C or less. This makes the effects of the present invention described above even more pronounced.

[0028] [1-1] Diallylphthalate resin The resin molding material of the present invention comprises a diallyl phthalate resin.

[0029] The diallyl phthalate resin contained in the resin molding material of the present invention includes not only those having a structure in which diallyl phthalate, which is an ester of phthalic acid and allyl alcohol, is polymerized at the allyl group of diallyl phthalate, but also those in which at least a portion of the diallyl phthalate as a constituent monomer is replaced by a compound in which at least a portion of the hydrogen atoms on the benzene ring of phthalic acid is replaced by halogen atoms such as chlorine and bromine (hereinafter also referred to as "substituted diallyl phthalate"), or compounds in which all or part of the unsaturated bonds present in the molecule of diallyl phthalate / substituted diallyl phthalate are hydrogenated (hereinafter also referred to as "hydrogenated diallyl phthalate compound").

[0030] In the following explanation, diallyl phthalate, the above-mentioned substituted diallyl phthalate, and the above-mentioned hydrogenated diallyl phthalate compounds, as constituent monomers of diallyl phthalate resins, are collectively referred to as "diallyl phthalate monomers."

[0031] The diallyl phthalate resin may contain constituent monomers other than diallyl phthalate monomers. Examples of such constituent monomers include monoallyl phthalate and allyl alcohol, and one or more selected from these can be used in combination.

[0032] However, the proportion of diallyl phthalate monomers in the total constituent monomers of the diallyl phthalate resin is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more. This makes the effects of the present invention described above even more pronounced.

[0033] Examples of the phthalic acid include orthophthalic acid, isophthalic acid, and terephthalic acid, but isophthalic acid is preferred. In other words, the resin molding material of the present invention preferably contains diallyl isophthalate resin as the diallyl phthalate resin.

[0034] This makes the effects of the present invention described above even more pronounced. In particular, it is possible to impart superior heat resistance to molded articles obtained using resin molding materials.

[0035] Furthermore, diallyl isophthalate resins include not only those having a structure in which diallyl isophthalate, an ester of isophthalic acid and allyl alcohol, is polymerized at the allyl group of diallyl isophthalate, but also compounds in which at least a portion of the diallyl isophthalate as a constituent monomer, or at least a portion of the hydrogen atoms on the benzene ring of isophthalic acid, are substituted with halogen atoms such as chlorine and bromine (hereinafter also referred to as "substituted diallyl isophthalate"), or compounds in which all or part of the unsaturated bonds present in the molecule of diallyl isophthalate / substituted diallyl isophthalate are hydrogenated (hereinafter also referred to as "hydrogenated diallyl isophthalate compounds").

[0036] In the following explanation, diallyl isophthalate, the above-mentioned substituted diallyl isophthalate, and the above-mentioned hydrogenated diallyl isophthalate compounds, which are constituent monomers of diallyl isophthalate resins, will be collectively referred to as "diallyl isophthalate monomers."

[0037] The diallyl isophthalate resin may contain constituent monomers other than diallyl isophthalate monomers. Examples of such constituent monomers include monoallyl isophthalate and allyl alcohol, and one or more selected from these can be used in combination.

[0038] The weight-average molecular weight (measured by GPC and converted to standard polystyrene) of the diallyl phthalate resin is not particularly limited, but is preferably 15,000 to 70,000, more preferably 20,000 to 60,000, and even more preferably 25,000 to 55,000. This makes it possible to improve the fluidity of the resin molding material.

[0039] The iodine value of the diallyl phthalate resin is not particularly limited, but is preferably 30 to 110, more preferably 35 to 100, and even more preferably 40 to 90. This makes it possible to improve the fluidity of the resin molding material.

[0040] The softening point of the diallyl phthalate resin is not particularly limited, but is preferably 40°C to 100°C, more preferably 45°C to 90°C, and even more preferably 50°C to 80°C. This makes it possible to improve the fluidity of the resin molding material.

[0041] The content of diallyl phthalate resin in the resin molding material is preferably 18.0% by mass or more and 35.0% by mass or less, more preferably 20.0% by mass or more and 33.0% by mass or less, even more preferably 23.0% by mass or more and 32.0% by mass or less, and most preferably 25.0% by mass or more and 32.0% by mass or less.

[0042] This makes it easier to suitably satisfy the above-mentioned conditions for the comparative tracking index CTI and glass transition temperature Tg, resulting in improved tracking resistance, heat resistance, and moldability.

[0043] In this specification, unless otherwise specified, the content [mass%] of a given component in the resin molding material refers to its content relative to the total solid content of the resin molding material. The solid content of the resin molding material refers to the non-volatile components in the resin molding material, which is the remainder after excluding volatile components such as water and solvents.

[0044] [1-2] diallyl phthalate compounds in their non-polymerized state The resin molding material of the present invention may contain a diallyl phthalate compound in a non-polymerized state.

[0045] Examples of non-polymerized diallyl phthalate compounds include diallyl phthalate, which is an ester of phthalic acid and allyl alcohol; compounds in which at least some of the hydrogen atoms on the benzene ring of phthalic acid constituting diallyl phthalate are replaced with halogen atoms such as chlorine and bromine (hereinafter also referred to as "substituted diallyl phthalate compounds"); and compounds in which all or some of the unsaturated bonds present in the molecule of the diallyl phthalate / substituted diallyl phthalate compound are hydrogenated (hereinafter also referred to as "hydrogenated diallyl phthalate compounds"). One or more of these can be selected and used in combination.

[0046] Furthermore, examples of phthalic acids that constitute the non-polymerized diallyl phthalate compound include orthotypes such as phthalic anhydride and orthophthalic acid, metatypes such as isophthalic acid, and paratypes such as terephthalic acid. One or more of these can be selected and used in combination.

[0047] Preferred specific examples of non-polymerized diallyl phthalate compounds include diallyl orthophthalate, diallyl isophthalate, and diallyl terephthalate, with diallyl isophthalate being the most preferred. This makes the effects of the present invention described above even more pronounced.

[0048] The content of the non-polymerized diallyl phthalate compound in the resin molding material is preferably 0.1% by mass or more and 3.5% by mass or less, more preferably 0.15% by mass or more and 2.5% by mass or less, and even more preferably 0.2% by mass or more and 2.3% by mass or less. This makes the effects described above even more pronounced.

[0049] The sum of the content of diallyl phthalate resin and the content of non-polymerized diallyl phthalate compound in the resin molding material is preferably 21.0% by mass or more and 34.0% by mass or less, more preferably 24.2% by mass or more and 33.5% by mass or less, and even more preferably 26.5% by mass or more and 32.0% by mass or less. This can make the effects described above even more pronounced.

[0050] The content of the non-polymerized diallyl phthalate compound is preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 0.3 parts by mass or more and 8 parts by mass or less, and even more preferably 0.5 parts by mass or more and 6 parts by mass or less, per 100 parts by mass of the sum of the content of the diallyl phthalate resin and the content of the non-polymerized diallyl phthalate compound.

[0051] This allows for a reduction in the diallyl phthalate resin content while maintaining favorable fluidity in the resin molding material. Furthermore, it enables the creation of molded articles, particularly thin-walled molded articles, with excellent flatness. Although the detailed mechanism for achieving these excellent effects is not entirely clear, it is believed that using a low-viscosity diallyl phthalate resin while reducing its content results in high fluidity and a reduction in the pressure gradient during molding.

[0052] [1-3] Aluminum hydroxide The resin molding material of the present invention preferably contains aluminum hydroxide.

[0053] This allows for improved tracking resistance. Furthermore, it enables optimal fluidity of the resin molding material and superior mechanical strength of the molded product.

[0054] The shape of aluminum hydroxide is not particularly limited, but for example, it may be particulate.

[0055] The average particle size of aluminum hydroxide is preferably 5 μm or more and 50 μm or less, more preferably 6 μm or more and 25 μm or less, and even more preferably 7 μm or more and 20 μm or less.

[0056] This makes it possible to further improve the heat resistance and mechanical strength of molded articles obtained using resin molding materials.

[0057] In this specification, unless otherwise specified, the average particle size refers to the average particle size based on volume. The average particle size can be determined by measurement using a commercially available laser diffraction particle size distribution analyzer (for example, Shimadzu Corporation's SALD-7000).

[0058] The aluminum hydroxide content in the resin molding material is preferably 5.0% by mass or more and 43.0% by mass or less, more preferably 6.0% by mass or more and 40.0% by mass or less, even more preferably 10.0% by mass or more and 35.0% by mass or less, and most preferably 15.0% by mass or more and 30.0% by mass or less.

[0059] This makes it easier to suitably satisfy the conditions for the comparative tracking index (CTI) and glass transition temperature (Tg) mentioned above, resulting in improved tracking resistance, heat resistance, and moldability. Furthermore, it improves the fluidity of the resin molding material and enhances the mechanical strength of the molded article obtained using the resin molding material.

[0060] The content of aluminum hydroxide is preferably 20 parts by mass or more and 200 parts by mass or less, more preferably 40 parts by mass or more and 140 parts by mass or less, and even more preferably 50 parts by mass or more and 120 parts by mass or less, per 100 parts by mass of the sum of the content of the diallyl phthalate resin and the content of the diallyl phthalate compound in its non-polymerized state. This makes the effects described above even more pronounced.

[0061] Figure 1 is a graph showing the total content (sum of blending amounts) of diallyl phthalate resin and non-polymerized diallyl phthalate compounds on the horizontal axis (x axis) and the content (amount blended) of aluminum hydroxide on the vertical axis (y axis) for resin molding materials.

[0062] In the resin molding material of the present invention, it is preferable that the condition y > 1.07x - 27.6 (where 20 ≤ x ≤ 45) is satisfied when x is the total content [mass%] of the diallyl phthalate resin and the non-polymerized diallyl phthalate compound and y is the content [mass%] of the aluminum hydroxide. In other words, it is preferable that the coordinate (x,y) representing the total content x [mass%] of the diallyl phthalate resin and the non-polymerized diallyl phthalate compound and the content y [mass%] of the aluminum hydroxide in the resin molding material of the present invention lies in a region above the line segment L represented by y = 1.07x - 27.6 (where 20 ≤ x ≤ 45).

[0063] This makes it easier to suitably satisfy the above-mentioned conditions for the comparative tracking index CTI and glass transition temperature Tg, resulting in improved tracking resistance, heat resistance, and moldability.

[0064] [1-4]Inorganic filler The resin molding material of the present invention may further contain a filler. While inorganic and organic fillers can be used as fillers, inorganic fillers are preferred from the viewpoint of electrical insulation.

[0065] The inorganic filler is not particularly limited, but for example, fibrous inorganic fillers such as glass fibers can be suitably used.

[0066] The glass fibers are not particularly limited, but examples include A-glass, C-glass, D-glass, E-glass, R-glass, S-glass, T-glass, AR-glass, etc., and one or more types selected from these can be used in combination.

[0067] The average fiber diameter of the glass fibers is not particularly limited, but is preferably 3 μm to 30 μm, more preferably 5 μm to 20 μm, and even more preferably 6 μm to 15 μm.

[0068] This improves the workability during the manufacturing of resin molding materials and makes the resulting molded articles have superior mechanical strength. Specifically, by setting the average fiber diameter to be above the lower limit, the mechanical strength of the resulting molded articles can be improved. Furthermore, by setting the average fiber diameter to be below the upper limit, when using a kneading roll during the manufacturing of resin molding materials, it is possible to suppress a decrease in kneading performance due to reduced followability to the roll.

[0069] The glass fiber content is preferably 15 parts by mass or more and 300 parts by mass or less, more preferably 17 parts by mass or more and 280 parts by mass or less, and even more preferably 20 parts by mass or more and 250 parts by mass or less, per 100 parts by mass of diallyl phthalate resin.

[0070] This allows for improved fluidity and linear expansion anisotropy of the resulting molded article while maintaining sufficient mechanical strength.

[0071] Furthermore, the resin molding material may include non-fibrous inorganic fillers, such as spherical, plate-shaped, or irregularly shaped inorganic fillers.

[0072] Non-fibrous inorganic fillers are not particularly limited, but examples include magnesium hydroxide, calcium carbonate, calcined clay, uncalcined clay, wollastonite, talc, silica, diatomaceous earth, alumina, magnesium oxide, barium sulfate, etc., and one or more selected from these can be used in combination.

[0073] The particle size of the non-fibrous inorganic filler is not particularly limited, but is preferably such that it is permeable to the entire 100-mesh and has a volume-average particle size of 0.5 μm to 80 μm, more preferably such that it is permeable to the entire 100-mesh and has a volume-average particle size of 1 μm to 30 μm, and even more preferably such that it is permeable to the entire 100-mesh and has a volume-average particle size of 5 μm to 20 μm.

[0074] This allows for improved mechanical strength of the resulting molded article. Specifically, by setting the particle size of the non-fibrous inorganic filler to above the lower limit, mechanical strength can be improved. Furthermore, since the anisotropy in the coefficient of thermal expansion of the molded article can be reduced, a molded article with excellent dimensional stability can be realized. On the other hand, by setting the particle size to below the upper limit, variations in mechanical strength can be reduced more effectively.

[0075] The content of non-fibrous inorganic filler is preferably 15 parts by mass or more and 300 parts by mass or less, more preferably 17 parts by mass or more and 280 parts by mass or less, and even more preferably 20 parts by mass or more and 250 parts by mass or less, per 100 parts by mass of diallyl phthalate resin.

[0076] This makes it possible to improve the fluidity, rigidity, anisotropy, and other properties of the resin molding material, and to realize a molded product with a particularly excellent balance of these properties.

[0077] The resin molding material may contain both fibrous inorganic fillers and non-fibrous inorganic fillers as fillers. By including granular or amorphous non-fibrous inorganic fillers, the orientation of the inorganic fillers can be reduced, thereby reducing the anisotropy of the linear expansion of the molded article. In addition, the rigidity of the molded article can be increased because the filler content can be increased.

[0078] The filler content is preferably 30 parts by mass or more and 500 parts by mass or less, more preferably 35 parts by mass or more and 450 parts by mass or less, and even more preferably 40 parts by mass or more and 400 parts by mass or less, per 100 parts by mass of diallyl phthalate resin.

[0079] This allows for improved fluidity of the resin molding material and enhanced mechanical strength of the resulting molded product.

[0080] [1-5] Polymerization initiator The resin molding material of the present invention may further contain a polymerization initiator.

[0081] The polymerization initiator is not particularly limited, and for example, known organic peroxides can be used.

[0082] The organic peroxide is not particularly limited, but examples include dialkyl peroxides, hydroperoxides, and peroxyesters, and one or more selected from these can be used in combination.

[0083] The organic peroxide may include, for example, one whose decomposition temperature for obtaining a half-life of 1 minute is between 150°C and 200°C.

[0084] This allows for optimal mixing of each component at a temperature where the polymerization initiator does not decompose, thereby enabling the production of a resin molding material in which the reaction mediated by the polymerization initiator is suppressed. As a result, a resin molding material with excellent fluidity can be obtained.

[0085] The polymerization initiator content is preferably 0.1 parts by mass or more and 6.0 parts by mass or less, more preferably 0.5 parts by mass or more and 5.0 parts by mass or less, and even more preferably 0.8 parts by mass or more and 4.0 parts by mass or less, per 100 parts by mass of diallyl phthalate resin. This makes the effects described above even more pronounced.

[0086] [1-6] Polymerization inhibitors The resin molding material of the present invention may further contain a polymerization inhibitor.

[0087] Polymerization inhibitors have the function of inhibiting the polymerization of resins, which can delay the start of curing of resin molding materials. Furthermore, by adjusting the content, high fluidity can be obtained without substantially affecting the curing time during molding.

[0088] Polymerization inhibitors are not particularly limited, but examples include quinones such as hydroquinone, p-methoxyphenol, and 2,6-di-tert-butyl-4-methylphenol; phenols such as 2,2'-methylenebis(6-tert-butyl-3-methylphenol), 4,4'-butylidenebis-16-tert-butyl-3-methylphenol, 4,4-theobis(6-tert-butyl-3-methylphenol), and p-nitrosophenol; sulfides such as diisopropylxanthogene sulfide; ammonium salts such as N-nitrosophenylhydroxylamine ammonium salt; 1,1-diphenyl-2-bicrylhydrazyl; and 1,3,5-triphenylfeldazyl. One or more selected from these can be used in combination. Among these, hydroquinone is preferred.

[0089] The polymerization inhibitor content is preferably 0.005 parts by mass or more and 0.15 parts by mass or less, more preferably 0.007 parts by mass or more and 0.10 parts by mass or less, and even more preferably 0.010 parts by mass or more and 0.080 parts by mass or less, per 100 parts by mass of diallyl phthalate resin.

[0090] This makes it possible to improve the fluidity of the resin molding material, maintain the curing speed, and improve moldability.

[0091] [1-7] Coupling agents The resin molding material of the present invention may further contain a coupling agent.

[0092] This makes it possible to suppress the aggregation of any inorganic filler, for example, and to improve the fluidity of the resin molding material.

[0093] The coupling agent is not particularly limited, but examples include various silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and methacrylicsilane, as well as known coupling agents such as titanium compounds, aluminum chelates, and aluminum / zirconium compounds. One or more of these can be selected and used in combination.

[0094] In particular, coupling agents having a (meth)acrylic group, such as methacrylatesilane, are preferred. This makes the effects described above even more pronounced.

[0095] The content of the coupling agent in the resin molding material is preferably 0.1% by mass or more and 10.0% by mass or less, more preferably 0.2% by mass or more and 5.0% by mass or less, and even more preferably 0.3% by mass or more and 3.0% by mass or less. This makes the effects described above even more pronounced.

[0096] [1-8] Flame retardants The resin molding material of the present invention may further contain a flame retardant.

[0097] The flame retardant is not particularly limited, but examples include halogen compounds, antimony compounds, metal hydroxides, uncalcined clay, boron compounds, nitrogen compounds, etc., and one or more selected from these can be used in combination.

[0098] Examples of metal hydroxides include magnesium hydroxide. Examples of boron compounds include boric acid and zinc borate.

[0099] These materials exhibit flame retardancy by decomposing during combustion, generating water, and absorbing heat from the combustion field. When using them, the impact on properties other than flame retardancy should be considered and used accordingly.

[0100] Examples of nitrogen compounds include melamine monomers, melamine resins, and melamine cyanurates, and one or more of these can be used in combination. Nitrogen compounds can exhibit flame retardancy by releasing an inert gas during combustion, diluting the oxygen concentration in the combustion field, and stopping the combustion.

[0101] The flame retardant content in the resin molding material is preferably 0.1% by mass or more and 15.0% by mass or less, more preferably 0.5% by mass or more and 12.0% by mass or less, and even more preferably 1.0% by mass or more and 10.0% by mass or less.

[0102] This allows for better flame retardancy and more favorable curability of the molded article.

[0103] Furthermore, the resin molding material may substantially contain at least one compound selected from the group consisting of halogen compounds, antimony compounds, red phosphorus, and organophosphorus compounds.

[0104] For example, halogen compounds, antimony compounds, red phosphorus, organophosphorus compounds, etc., can be used as flame retardants. However, it is preferable that the resin molding material substantially does not contain at least one selected from the group consisting of halogen compounds, antimony compounds, red phosphorus, and organophosphorus compounds as a flame retardant, and more preferably that it does not contain any halogen compounds, antimony compounds, red phosphorus, or organophosphorus compounds as a flame retardant. In other words, it is more preferable to use a flame retardant that is non-halogen, non-antimony, and non-phosphorus. This makes it possible to create cleaner, more environmentally friendly resin molding materials.

[0105] [1-9] Release agent The resin molding material of the present invention may further contain a mold release agent. This improves the release properties after molding.

[0106] While not particularly limited, examples of release agents include natural waxes such as carnauba wax, synthetic waxes such as montanic acid ester wax, higher fatty acids such as zinc stearate and calcium stearate and their metal salts, and paraffin. One or more of these can be selected and used in combination.

[0107] The content of the mold release agent in the resin molding material is preferably 0.1% by mass or more and 3.0% by mass or less, more preferably 0.2% by mass or more and 2.5% by mass or less, and even more preferably 0.3% by mass or more and 2.0% by mass or less. This makes the effects described above even more pronounced.

[0108] [1-10] Other ingredients The resin molding material of the present invention may contain components other than those described above. Hereinafter, such components will also be referred to as "other components".

[0109] Other components include, for example, resins other than diallyl phthalate resin, compatibilizers, plasticizers, curing accelerators, elastomers, colorants, antioxidants, UV absorbers, light stabilizers, softeners, modifiers, rust inhibitors, electromagnetic wave absorbers, surface lubricants, corrosion inhibitors, heat stabilizers, lubricants, primers, antistatic agents, crosslinking agents, catalysts, leveling agents, thickeners, dispersants, anti-aging agents, hydrolysis inhibitors, etc., and one or more of these can be selected and used in combination.

[0110] Resins other than diallyl phthalate resin are not particularly limited, but examples include unsaturated polyester resins.

[0111] However, the content of resins other than diallyl phthalate resin in the resin molding material is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 0.5% by mass or less.

[0112] The curing accelerator is not particularly limited, but examples include magnesium oxide and calcium hydroxide, and one or more selected from these can be used in combination.

[0113] The elastomer is not particularly limited, but examples include styrene-butadiene rubber, butadiene rubber, acrylic rubber, nitrile rubber, isoprene rubber, ethylene propylene rubber, polyisobutylene, polyurethane, polyvinyl butyral, and one or more of these can be used in combination.

[0114] The content of other components in the resin molding material is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 1.0% by mass or less.

[0115] [1-11] Shape of resin molding material The shape of the resin molding material is not particularly limited and may be any shape, such as pellets or granules.

[0116] [1-12] Method for manufacturing resin molding materials The resin molding material of the present invention can be manufactured, for example, by mixing the above-mentioned components in predetermined proportions, melt-kneading them using a heated roll, cone kneader, twin-screw extruder, etc., and then crushing and classifying them after cooling.

[0117] Furthermore, each component of the resin molding material may be added simultaneously during compounding, or each component may be added at different times.

[0118] [1-13] Method for manufacturing molded articles (molding method using resin molding material), applications A molded body can be obtained by molding the resin molding material of the present invention using various molding methods such as injection molding, transfer molding, and compression molding. The shape of the molded body is not particularly limited and may be, for example, in the form of a sheet.

[0119] The applications of the resin molding material of the present invention are not particularly limited, but because it possesses excellent tracking resistance and heat resistance, it is suitably used as a material for electrical and electronic components. Specifically, it is preferably used, for example, to seal semiconductor elements, substrates, terminals, coils, magnets, and the like.

[0120] Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto. [Examples]

[0121] The present invention will be described in detail below based on specific examples, but the present invention is not limited thereto. In the following examples, unless the temperature conditions are specified, the processes and measurements were performed at room temperature (23°C).

[0122] [2] Manufacturing of resin molding materials <Examples 1-6, Comparative Examples 1-2> The components were mixed according to the mixing ratios shown in Table 1, melt-kneaded using a heated roller at 90°C for 5 minutes, then removed and pulverized into granules to obtain a resin molding material.

[0123] Table 1 summarizes the composition of the resin molding materials for each of the above examples and comparative examples. The raw material components shown in Table 1 are as follows:

[0124] (Diallylphthalate resin 1) • Diallyl isophthalate resin: Manufactured by Osaka Soda Co., Ltd., Daiso Isodapp, weight-average molecular weight (polystyrene equivalent): 3 x 10 4 ~5×10 4 Iodine value: 75-90, softening point: 50°C-80°C, having the chemical structure shown in formula (1) below.

[0125] [ka]

[0126] (Diallylphthalate resin 2) • Diallyl orthophthalate resin: Manufactured by Osaka Soda Co., Ltd., Daiso DAP K, weight-average molecular weight (polystyrene equivalent): 2 x 10 4 ~3×10 4 Iodine value: 50-60, softening point: 65°C-100°C, having the chemical structure shown in formula (2) below.

[0127] [ka]

[0128] (Diallyl phthalate compound in its non-polymerized state) • Diallyl isophthalate: Manufactured by Osaka Soda Co., Ltd., product name: Daiso Dapp 100 monomer, having the chemical structure shown in formula (3) below.

[0129] [ka]

[0130] (aluminum hydroxide) • Aluminum hydroxide: Average particle size 10 μm

[0131] (Polymerization initiator) • Polymerization initiator: Organic peroxide (thermal decomposition temperature (decomposition temperature to obtain a half-life of 1 minute): 175°C)

[0132] (Polymerization inhibitor) • Polymerization inhibitor: 4-tert-butylpyrocatechol

[0133] (filling material) • Filler 1: Manufactured by NSG, product name: RES015-BM42, average fiber diameter: 11 μm • Filler 2: Manufactured by Denka Co., Ltd., Product name: FB-5D, Average particle size: 4.7 μm

[0134] (Flame retardant) • Flame retardant: A mixture of ethylenebistetrabromophthalimide and antimony trioxide.

[0135] (Release agent) • Release agent: Calcium stearate

[0136] (Pigment) Pigment: Carbon Black

[0137] (Coupling agent) • Coupling agent: Manufactured by Shin-Etsu Chemical Co., Ltd., Product name: KBM-503

[0138] [Table 1]

[0139] [3] Characterization The properties of the resin molding materials obtained in each of the above examples and comparative examples were evaluated by the following method.

[0140] [3-1] Glass transition temperature As an indicator of heat resistance, we attempted to measure the glass transition temperature (Tg).

[0141] First, the resin molding materials of each of the above examples and comparative examples were injected and molded using a transfer molding machine (Towa Seiki Co., Ltd. "TEP50-70") under the conditions of a mold temperature of 165°C, an injection pressure of 5 MPa, and a curing time of 240 seconds to obtain a molded product of 80 mm × 10 mm × 4 mm. Next, the obtained molded product was post-cured at 180°C for 8 hours, and an attempt was made to obtain a test piece of 10 mm × 10 mm × 4 mm from the molded product.

[0142] The glass transition temperature was then determined from the obtained test specimens using a thermomechanical analyzer (Seiko Instruments, TMA100) under the conditions of a measurement temperature range of 0°C to 400°C and a heating rate of 5°C / min. Specifically, the glass transition temperature was defined as the temperature at the intersection of the linear portions on the low-temperature and high-temperature sides when the elongation / compression amount was plotted on the vertical axis and temperature on the horizontal axis, based on measurements using a thermomechanical analyzer. A higher glass transition temperature indicates superior heat resistance.

[0143] [3-2] Tracking resistance As an indicator of tracking resistance, we attempted to measure the comparative tracking index (CTI).

[0144] First, the resin molding materials of each of the above examples and comparative examples were transferred and molded under the conditions of a mold temperature of 165°C, an injection pressure of 5 MPa, and a curing time of 240 seconds, in an attempt to obtain a circular molded body (test piece) with a diameter of 50 mm and a thickness of 3 mm.

[0145] Then, the comparative tracking index was measured for the obtained test specimens. Specifically, for voltages of 600V or less, measurements were performed in accordance with the test method specified in the international standard IEC60112. For voltages exceeding 600V, the electrodes used in the test method specified in the international standard IEC60112 were rotated 180° around the longitudinal direction of the electrodes as the axis of rotation, and the electrodes were fixed so that the angle between the molded body and the electrodes was 30° before measurement. A higher comparative tracking index (CTI) value indicates superior tracking resistance.

[0146] [3-3] Formability When attempting to manufacture the test specimens as described in [3-1] above, those that were able to produce a molded product of 80mm x 10mm x 4mm were evaluated as "○", and those that were not able to produce a molded product of 80mm x 10mm x 4mm were evaluated as "×".

[0147] The evaluation results described above are summarized in Table 2.

[0148] [Table 2]

[0149] As is clear from Table 2, the present invention yielded a resin molding material with excellent tracking resistance, heat resistance, and moldability.

[0150] Figure 2 is a graph showing the total content (sum of blending amounts) of diallyl phthalate resin and non-polymerized diallyl phthalate compound on the horizontal axis (x axis) and the content (amount blended) of aluminum hydroxide on the vertical axis (y axis) for the resin molding materials of each example and each comparative example.

[0151] In Examples 1-4 and 6, particularly good results were obtained in Examples 1-4 and 6, where the coordinates (x,y) representing the total content x [mass%] of diallyl phthalate resin and non-polymerized diallyl phthalate compound, and the content y [mass%] of aluminum hydroxide in the resin molding material, lie above the line segment L represented by y = 1.07x - 27.6 (where 20 ≤ x ≤ 45). In other words, in Examples 1-4 and 6, which satisfy the condition y > 1.07x - 27.6 (where 20 ≤ x ≤ 45), particularly good results were obtained.

[0152] In contrast, satisfactory results were not obtained in the comparative examples. In particular, in Comparative Example 2, test specimens could not be obtained as described in [3-1] and [3-2] above, and therefore these measurements could not be performed.

[0153] Furthermore, resin molding materials were manufactured in the same manner as in the above examples, except that the diallyl phthalate resin used had various weight-average molecular weights within the range of 15,000 to 70,000, various iodine values ​​within the range of 60 to 110, and various softening points within the range of 40°C to 100°C. These materials were then evaluated in the same manner as described above, and the same favorable results were obtained.

[0154] Furthermore, resin molding materials were manufactured in the same manner as in the above examples, except that aluminum hydroxide with an average particle size of 5 μm to 50 μm was used, and these were evaluated in the same manner as above, and good results were obtained, similar to those described above.

[0155] Furthermore, when a non-polymerized diallyl phthalate compound was used, and diallyl orthophthalate was used instead of diallyl isophthalate, resin molding materials were produced in the same manner as in the above examples, and these were evaluated in the same manner as above, and good results were obtained, similar to those described above. [Explanation of Symbols]

[0156] L: line segment

Claims

1. A resin molding material containing diallyl phthalate resin, The comparative tracking index CTI obtained by (Method 1) below is 800V or higher, A resin molding material characterized by having a glass transition temperature Tg of 200°C or higher and 300°C or lower. (Method 1) Under the conditions of a mold temperature of 165°C, an injection pressure of 5 MPa, and a curing time of 240 seconds, a resin molding material is transfer-molded to obtain a circular molded body with a diameter of 50 mm and a thickness of 3 mm. The comparative tracking index of the obtained molded body is then measured. At voltages of 600 V or less, the measurement is performed in accordance with the test method specified in the international standard IEC 60112. At voltages exceeding 600 V, the electrode in the test method specified in the international standard IEC 60112 is rotated 180° with the longitudinal direction of the electrode as the axis of rotation, and the electrode is fixed so that the angle between the molded body and the electrode becomes 30° before measurement.

2. The resin molding material according to claim 1, further comprising a diallyl phthalate compound in a non-polymerized state.

3. The resin molding material according to claim 2, wherein the non-polymerized diallyl phthalate compound is diallyl isophthalate.

4. It further contains aluminum hydroxide, When x is the total content [mass%] of the diallyl phthalate resin and the non-polymerized diallyl phthalate compound, and y is the content [mass%] of the aluminum hydroxide, A resin molding material according to claim 2 or 3 that satisfies the condition y > 1.07x - 27.6 (where 20 ≤ x ≤ 45).

5. The resin molding material according to claim 1 or 2, wherein the diallyl phthalate resin is a diallyl isophthalate resin.

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