JP7075735B2 - Resin composition and composition for resin production - Google Patents

Description

The present invention relates to a resin composition and a composition for producing a resin.

In order to protect from dew condensation and contamination, an object such as an electric / electronic component is sealed with a resin composition such as polyurethane (Patent Document 1). Such a resin composition is often blended with an inorganic filler for improving flame retardancy.

Japanese Unexamined Patent Publication No. 2008-231348 Japanese Unexamined Patent Publication No. 2001-352156

However, when the inorganic filler is blended, there is a problem that the weight of the resin composition becomes large. For example, even if the blending amount of the inorganic filler in the resin composition is adjusted, it is difficult to achieve both flame retardancy and lightness of the resin composition. Further, there is a problem that the dielectric constant of the resin composition increases beyond an acceptable range due to the addition of the inorganic filler to the resin composition.

The present invention has been made to solve the above-mentioned problems, and an object thereof is for producing resin compositions and resins having improved flame retardancy and reduced dielectric constant while suppressing an increase in weight due to an inorganic filler. Is to provide the composition.

As a result of diligent studies to solve the above problems, the inventors of the present invention have found that the above problems can be solved by using a certain material, and have completed the present invention.

That is, the resin composition of the present invention is a resin composition containing a resin (X), an inorganic filler (C), and a hollow filler (D) having a hollow portion inside and having a resin outer shell. The resin (X) is a polyurethane resin produced by the reaction of the hydroxyl group-containing compound (A) and the isocyanate group-containing compound (E), and the hydroxyl group-containing compound (A) is a castor oil-based polyol and a polybutadiene polyol. The inorganic filler (C) is one or more selected from aluminum hydroxide and magnesium hydroxide, and the inorganic filler (C) is the inorganic filler (C). A resin composition containing 45 to 70 parts by mass with respect to 100 parts by mass of the resin composition and 0.5 to 5 parts by mass with respect to 100 parts by mass of the resin composition.

Further, the composition for resin production of the present invention is a composition (Y) capable of producing a resin composition by mixing with other materials, and has an inorganic filler (C) and a hollow portion inside. A resin-producing composition (Y) containing a hollow filler (D) having a resin outer shell, wherein the composition (Y) contains a hydroxyl group-containing compound (A) and is a hydroxyl group-containing compound (A). Contains one or more selected from castor oil-based polyols and polybutadiene polyols, and the inorganic filler (C) is one or more selected from aluminum hydroxide and magnesium hydroxide. , The inorganic filler (C) is contained in an amount of 45 to 70 parts by mass based on 100 parts by mass of the resin composition, and the hollow filler (D) is contained in an amount of 0.5 to 5 parts by mass based on 100 parts by mass of the resin composition. , A composition for producing a resin.

INDUSTRIAL APPLICABILITY According to the present invention, flame retardancy can be improved while suppressing an increase in the weight of the resin composition, and the dielectric constant of the resin composition can be further suppressed.

First, the contents of the embodiments of the present invention are listed.

(1) The resin composition according to the embodiment of the present invention comprises a resin (X), an inorganic filler (C), and a hollow filler (D) having a hollow portion inside and having a resin outer shell. include. With such a configuration, for example, the weight of the entire resin composition can be reduced while imparting flame retardancy to the resin composition by the inorganic filler (C). Further, since the inside of the hollow filler (D) is a gas having a lower relative permittivity than the resin (X), the dielectric constant of the resin composition can be lowered. Therefore, it is possible to improve the flame retardancy while suppressing the increase in the weight of the resin composition, and further suppress the dielectric constant of the resin composition.

(2) Preferably, the resin composition contains 45 to 70 parts by mass of the inorganic filler (C) with respect to 100 parts by mass of the resin composition, and 100 parts by mass of the hollow filler (D). It contains 0.5 to 5 parts by mass. With such a configuration, it is possible to moderately reduce the weight of the resin composition and suppress the dielectric constant while imparting flame retardancy to the resin composition.

(3) The average particle size of the hollow filler (D) is preferably 30 μm to 100 μm. With such a configuration, it is possible to moderately reduce the weight of the resin composition and suppress the dielectric constant while imparting flame retardancy to the resin composition.

(4) Preferably, the resin composition is used for encapsulating electrical and electronic parts. With such a configuration, it is possible to appropriately protect the electric / electronic parts and further suppress the ignition of the unit while suppressing the weight increase of the unit including the electric / electronic parts. Further, by suppressing the dielectric constant, it is possible to suppress the influence of the resin composition on the high frequency circuit, the wireless communication unit and the like.

(5) The resin composition according to the embodiment of the present invention is an electric / electronic component sealed with the resin composition according to (4) above. With such a configuration, it is possible to appropriately protect the electric / electronic parts and further suppress the ignition of the unit while suppressing the weight increase of the unit including the electric / electronic parts. Further, by suppressing the dielectric constant, it is possible to suppress the influence of the resin composition on the high frequency circuit, the wireless communication unit and the like.

(6) The composition for resin production according to the embodiment of the present invention is a composition (Y) capable of producing a resin composition by mixing with other materials, and has an inorganic filler (C) and an inside. Contains a hollow filler (D) having a hollow portion and a resin outer shell. With such a configuration, the composition (Y) can be used to produce a resin composition having improved flame retardancy while suppressing an increase in the weight of the resin composition and further suppressing the dielectric constant of the resin composition. can.

(7) Preferably, the inorganic filler (C) is contained in an amount of 50 to 80 parts by mass with respect to 100 parts by mass of the resin-producing composition, and the hollow filler (D) is contained in an amount of 100 parts by mass with respect to 100 parts by mass of the resin-producing composition. Contains 0.5 to 5 parts by mass. With such a configuration, it is possible to produce a resin composition having a flame retardancy, an appropriate weight reduction, and a reduced dielectric constant.

(8) The average particle size of the hollow filler (D) is preferably 30 μm to 100 μm. With such a configuration, it is possible to produce a resin composition having a flame retardancy, an appropriate weight reduction, and a reduced dielectric constant.

(9) Preferably, the hollow filler (D) has thermal expansion property. With such a configuration, for example, since it expands appropriately due to the heat applied when producing the resin composition, it is possible to produce a resin composition which is moderately lightweight while imparting flame retardancy and has a reduced dielectric constant. can. In addition, the volume of the resin-producing composition before heating can be suppressed.

Hereinafter, embodiments of the present invention will be described in detail.

[First Embodiment]
In the first embodiment, a polyurethane resin composition will be described as an example of the resin composition according to the present invention. The polyurethane resin composition in the present embodiment is formed by blending a hydroxyl group-containing compound (A), an inorganic filler (C), a hollow filler (D), and an isocyanate group-containing compound (E).

The hydroxyl group-containing compound (A) in the present embodiment is not particularly limited, and is, for example, a castor oil-based polyol, a polyether polyol, a polymer polyol, a low molecular weight glycol, a polyester polyol, a polybutadiene polyol, a polyisoprene polyol, and a dimer acid polyol. , Hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, etc. can be used. Moreover, you may use these in combination of 2 or more types.

The hydroxyl group-containing compound (A) preferably contains a castor oil-based polyol from the viewpoint of improving heat resistance. When the castor oil-based polyol is used in combination with another polyol, the blending amount of the castor oil-based polyol is preferably 30% by mass or more, more preferably 35% by mass or more, and 40% by mass of the total amount of the polyol to be used. It is more preferably mass% or more.

The castor oil-based polyol is not particularly limited, but includes castor oil, hydrogenated castor oil, ester exchanges of castor oil and other fats and oils, reactants of castor oil and polyhydric alcohol, and castor oil fatty acid and polyhydric alcohol. The esterified reaction products of the above, those obtained by addition-polymerizing alkylene oxide to these, and the like can be used. Moreover, you may use these in combination of 2 or more types.

The polyether polyol is not particularly limited, and for example, water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, diglycerin, pentaerythritol, ethylenediamine, methylglucoside, aromatic diamine, and sorbitol. , Sucrose, phosphoric acid and the like can be used as an initiator, and those obtained by ring-opening polymerization of alkylene oxide (hereinafter, may be referred to as "AO") can be used. Moreover, you may use these in combination of 2 or more types. The initiator is preferably water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane or hexanetriol as a starting material, and the AO is preferably ethylene oxide, propylene oxide or butylene oxide.

The polymer polyol is not particularly limited, and is, for example, a polymer polyol obtained by reacting the polyether polyol with an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst. Can be used. Moreover, you may use these in combination of 2 or more types.

The low molecular weight glycol is not particularly limited, and is, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. , 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1 , 3-Propylenediol, 2-methyl-1,3-Propylenediol and other aliphatic diols; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A and other alicyclic diols; Trifunctional or higher hydroxyl group-containing compounds such as glycerin, trimethylolpropane, and pentaerythritol can be used. Moreover, you may use these in combination of 2 or more types.

The polyester polyol is not particularly limited, but for example, a polyvalent hydroxyl group-containing compound and a polycarboxylic acid (aromatic polycarboxylic acid and an aliphatic polycarboxylic acid) or an anhydride and the lower alkyl (alkyl group having 1 to 1 to carbon atoms). 4) Condensation reaction products with ester-forming derivatives such as esters (phthalic acid anhydride, dimethyl terephthalate, etc.); polylactone polyols; polycarbonate polyols; Polyester polyols with (such as mono-or diglycerides of castor oil fatty acids, mono- or diesters of castor oil fatty acids and trimethylolpropane, mono-or diesters of castor oil fatty acids and polyoxypropylene glycol); An alkylene oxide (2 to 4 carbon atoms) added to the oil; a hydroxyl group-terminated prepolymer derived from castor oil and diphenylmethane diisocyanate, etc.] can be used. Moreover, you may use these in combination of 2 or more types.

The dimer acid polyol is not particularly limited, and for example, a diol, triol, polyalkylene glycol, a reaction product of polyalkylene triol and dimer acid, a reduced product of dimer acid, or the like can be used. Moreover, you may use these in combination of 2 or more types. The weight average molecular weight (Mw) of the dimer acid polyol is preferably 300 to 50,000. Further, the average number of functional groups per molecule of the dimer acid polyol is preferably 2 to 4. The hydroxyl value of the dimer acid polyol is preferably 2 mgKOH / g or more, and more preferably 30 mgKOH / g or more. The hydroxyl value of the dimer acid polyol is preferably 800 mgKOH / g or less, more preferably 500 mgKOH / g or less, and even more preferably 300 mgKOH / g or less.

The polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol are not particularly limited, but those usually used for polyurethane resin compositions can be used.

In the present embodiment, the hydroxyl group-containing compound (A) may be, for example, a hydroxyl group-terminated urethane prepolymer obtained by reacting a hydroxyl group-containing compound with an isocyanate group-containing compound.

From the viewpoint of moldability of the molded product, the content of the hydroxyl group-containing compound (A) is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more with respect to 100 parts by mass of the polyurethane resin composition. , 20 parts by mass or more is more preferable. Further, the content of the hydroxyl group-containing compound (A) is preferably 80 parts by mass or less, and preferably 70 parts by mass or less, based on 100 parts by mass of the polyurethane resin composition from the viewpoint of moldability of the molded product. More preferably, it is 60 parts by mass or less.

The isocyanate group-containing compound (E) in the present embodiment is not particularly limited, and is, for example, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, an aromatic polyisocyanate compound, an aromatic aliphatic polyisocyanate compound, or these. A modified version of the isocyanate compound can be used. Moreover, you may use these in combination of 2 or more types. As the isocyanate group-containing compound (E), an aliphatic polyisocyanate compound, an aromatic polyisocyanate compound, or a modified product of these isocyanate compounds is preferable.

Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2-. Methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate and the like can be used. Moreover, you may use these in combination of 2 or more types.

Examples of the alicyclic polyisocyanate compound include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexanediisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis (isocyanatemethyl) cyclohexane. Can be used. Moreover, you may use these in combination of 2 or more types.

Examples of the aromatic polyisocyanate compound include dialkyldiphenylmethane diisocyanate, tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (monomeric MDI), and polymethylene polyphenyl poly. Isocyanate (polymeric MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylenediocyanate, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate and the like can be used. Moreover, you may use these in combination of 2 or more types.

As the aromatic aliphatic polyisocyanate compound, xylylene diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylene diisocyanate and the like can be used. Moreover, you may use these in combination of 2 or more types.

As the modified product of the polyisocyanate compound, an isocyanurate modified product, a biuret modified product, an adduct modified product, a carbodiimide modified product, a bifunctional modified product and the like can be used. Moreover, you may use these in combination of 2 or more types.

Further, in the present embodiment, the isocyanate group-containing compound (E) may be, for example, an isocyanate group-terminated urethane prepolymer obtained by reacting a hydroxyl group-containing compound with an isocyanate group-containing compound.

The content of the isocyanate group-containing compound (E) is preferably 0.5 parts by mass or more, and is preferably 1 part by mass or more with respect to 100 parts by mass of the polyurethane resin composition from the viewpoint of moldability of the molded product. Is more preferable, and 1.5 parts by mass or more is further preferable. The content of the isocyanate group-containing compound (E) is preferably 80 parts by mass or less, and 70 parts by mass or less, based on 100 parts by mass of the polyurethane resin composition, from the viewpoint of moldability of the molded product. Is more preferable, 60 parts by mass or less is further preferable, and 50 parts by mass or less is further preferable.

In the present embodiment, the molar ratio (NCO / OH) of the hydroxyl group of the hydroxyl group-containing compound (A) to the isocyanate group of the isocyanate group-containing compound (E) is preferably 0.6 or more, preferably 0.8 or more. Is more preferable. If the molar ratio is smaller than this range, curing defects may occur and the heat resistance of the obtained resin may be lowered. The molar ratio is preferably 1.5 or less, more preferably 1.3 or less. If the molar ratio is larger than this range, curing failure may occur.

The inorganic filler (C) in the present embodiment can, for example, enhance the flame retardancy of the polyurethane resin composition. For example, when the object to be sealed by the polyurethane resin composition may ignite, the polyurethane resin composition is required to have flame retardancy. As the inorganic filler (C), hydroxide compounds such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, zinc borate, dosonite, silica and alumina can be used.

The blending amount of the inorganic filler (C) is preferably 45 parts by mass or more, preferably 50 parts by mass or more, with respect to 100 parts by mass of the polyurethane resin composition from the viewpoint of enhancing the flame retardancy of the polyurethane resin composition. Is more preferable. Further, the blending amount of the inorganic filler (C) is preferably 70 parts by mass or less with respect to 100 parts by mass of the polyurethane resin composition from the viewpoint of suppressing the weight of the polyurethane resin composition and the mixed viscosity at the time of production. , 65 parts by mass or less is more preferable. If the mixed viscosity at the time of manufacture is high, the workability tends to decrease.

The hollow filler (D) in the present embodiment has a hollow portion inside and a resin outer shell. By blending the hollow filler (D), it is possible to suppress an increase in the weight of the entire polyurethane resin composition due to the blending of the inorganic filler (C). Further, it is possible to suppress an increase in the dielectric constant of the polyurethane resin composition due to the blending of the inorganic filler (C).

The average particle size of the hollow filler (D) is preferably 30 μm or more, more preferably 40 μm or more, from the viewpoint of weight reduction of the polyurethane resin composition. The average particle size of the hollow filler (D) is preferably 100 μm or less, preferably 90 μm or less, from the viewpoint of reducing unevenness in the polyurethane resin composition and homogenizing the functions of the polyurethane resin composition. More preferably, it is more preferably 80 μm or less. The average particle size refers to the particle size at a volume-based cumulative 50% in the particle size distribution measured by the laser diffraction / scattering method, that is, D50 (median diameter). For the measurement of the particle size distribution, for example, a laser diffraction type particle size distribution measuring device (SALD-2200 manufactured by Shimadzu Corporation) is used.

The blending amount of the hollow filler (D) is preferably 0.5 parts by mass or more, and 0.8 parts by mass or more, based on 100 parts by mass of the polyurethane resin composition, from the viewpoint of weight reduction of the polyurethane resin composition. It is more preferable that the amount is 1 part by mass or more.

Increasing the blending ratio (mass) of the hollow filler (D) reduces the insulating property and flame retardancy of the polyurethane resin composition. Therefore, the blending amount of the hollow filler (D) is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and 3 parts by mass or less with respect to 100 parts by mass of the polyurethane resin composition. It is more preferable to have.

The outer shell of the hollow filler (D) is, for example, a thermoplastic resin. As the hollow filler (D), an expanded one and an unexpanded one can be used. For example, when the unexpanded hollow filler (D) is exposed to a certain temperature or higher, the internal cavity expands and the entire hollow filler (D) expands. On the other hand, the particle size hardly changes even if a certain amount of heat is applied to or cooled the expanded hollow filler (D).

When an unexpanded hollow filler (D) is used as the material of the polyurethane resin composition, for example, the hollow filler () is generated by the heat applied when the polyurethane resin composition is produced or the reaction heat generated by the polyurethane resin composition itself. D) can be inflated. Therefore, even when the unexpanded hollow filler (D) is used, the particle size of the hollow filler (D) can be set to a value suitable for the present embodiment in the manufacturing process of the polyurethane resin composition.

When both the inorganic filler (C) and the hollow filler (D) are blended in the polyurethane resin composition, the density in the polyurethane resin composition tends to be uneven, but the inorganic filler (C) and the hollow filler (D) tend to be uneven. By adjusting the ratio with, it is possible to suppress unevenness in the density in the polyurethane resin composition. Specifically, for example, the ratio of the inorganic filler (C) to the hollow filler (D) (hollow filler (D) / inorganic filler (C)) is 0.8% or more from the viewpoint of suppressing unevenness in density. It is preferably 1.0% or more, more preferably 1.3% or more, and even more preferably 1.3% or more. Further, the ratio is preferably 10% or less, more preferably 8% or less, still more preferably 5% or less, from the viewpoint of suppressing unevenness in density. By suppressing the unevenness of the density of the polyurethane resin composition, it is possible to suppress the unevenness of other properties such as flame retardancy and insulating property.

The polyurethane resin composition is generally produced by mixing a composition containing a hydroxyl group-containing compound (A) and a composition containing an isocyanate group-containing compound (E). Hereinafter, one of the composition containing the hydroxyl group-containing compound (A) and the composition containing the isocyanate group-containing compound (E) is also referred to as a composition for producing a resin composition (Y). The inorganic filler (C) and the hollow filler (D) may be blended in the composition for producing a resin composition (Y) before mixing. In that case, the blending amount of the inorganic filler (C) is preferably 50 parts by mass or more with respect to 100 parts by mass of the resin production composition (Y) from the viewpoint of enhancing the flame retardancy of the polyurethane resin composition. It is more preferably 55 parts by mass or more, more preferably 60 parts by mass or more, and further preferably 70 parts by mass or more. Further, the blending amount of the inorganic filler (C) is 80 parts by mass or less with respect to 100 parts by mass of the resin production composition (Y) from the viewpoint of suppressing the weight of the polyurethane resin composition and the mixed viscosity at the time of production. It is preferably 75 parts by mass or less, more preferably 70 parts by mass or less.

If the mixing ratio of the hollow filler (D) in the composition for producing the resin composition (Y) is increased, the insulating property and flame retardancy of the polyurethane resin composition are lowered. Therefore, the blending amount of the hollow filler (D) is preferably 5 parts by mass or less, and more preferably 4 parts by mass or less with respect to 100 parts by mass of the composition (Y) for resin production. Further, the blending amount of the hollow filler (D) is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the resin manufacturing composition (Y) from the viewpoint of weight reduction of the polyurethane resin composition. It is more preferably 8 parts by mass or more, and further preferably 1 part by mass or more.

A plasticizer (B) can be added to the polyurethane resin composition in the present embodiment. As the plasticizer (B), conventionally known ones used for polyurethane resins can be used, for example, phthalates such as dioctylphthalate, diisononylphthalate, diundecylphthalate, and diisononyl 1,2-cyclohexanedicarboxylate. Non-phthalate esters such as esters, adipic acid esters such as dioctyl adipate and diisononyl adipate, castor oil-based esters such as methyl acetyl ricinolate, butyl acetyl lysinolate, acetylated lysinolic acid triglyceride, acetylated poly lysinolic acid triglyceride, and birds. Trimellitic acid esters such as octyl lymericate and triisononyl trimerite, pyromellitic acid esters such as tetraoctylpyromerite and tetraisononylpyromerite, tricresyl phosphates, trisxylenyl phosphates, Phthalate esters such as cresyldiphenyl phosphate, xylenyl phosphate, and triphenyl phosphate can be used.

The blending amount of the plasticizer (B) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and more preferably 20 parts by mass or less with respect to 100 parts by mass of the polyurethane resin composition. More preferred. If the amount of the plasticizer is large, various physical properties such as the strength of the polyurethane resin composition may be deteriorated.

Various additives such as a catalyst, an antioxidant, a hygroscopic agent, an antifungal agent, and a silane coupling agent can be added to the polyurethane resin composition according to the present embodiment, if necessary. Examples of the silane coupling agent include alkoxysilanes, vinyl group-containing silane cuplinking agents, epoxy group-containing silane cuplinking agents, methacrylic group-containing silane cuplinking agents, and acrylic group-containing silane coupling agents.

The mixed viscosity of the polyurethane resin composition in the present embodiment at the time of production is preferably 5 Pa · s or less, and more preferably 4 Pa · s or less when a material at 25 ° C. is mixed, for example. If the mixed viscosity is equal to or less than the above value, it is good in terms of workability.

The polyurethane resin composition in the present embodiment can seal articles such as electrical and electronic parts, medical supplies, toys, and daily necessities.

<Example>
Hereinafter, the polyurethane resin composition of the present embodiment will be described in more detail based on Examples and Comparative Examples. The present invention is not limited thereto. In addition, "part" and "%" in this specification represent "part by mass" and "% by mass", respectively, unless otherwise specified.

The materials used in Examples and Comparative Examples are shown.
Hydroxy group-containing compound (A)
Hydroxy group-containing compound (A-1): Polybutadiene polyol (trade name: R-15HT, manufactured by Idemitsu Kosan Co., Ltd.)
Hydroxy group-containing compound (A-2): Castor oil-based polyol (trade name: castor oil D, manufactured by Itoh Oil Chemicals Co., Ltd.)

Plasticizer (B): Diundecylphthalate (Product name: Sunsociser DUP, manufactured by Shin Nihon Rika Co., Ltd.)

Inorganic filler (C)
-Inorganic filler (C-1): Aluminum hydroxide (trade name: C-305, manufactured by Sumitomo Chemical Co., Ltd.)
-Inorganic filler (C-2): Magnesium hydroxide
(Product name: ECOMAG, Tateho Chemical Industries, Ltd.)

Hollow filler (D)
-Hollow filler (D-1): Expanded, average particle size 33-55 μm
(Product name: Expandel 920 DE 40 d30, manufactured by Nippon Phillight Co., Ltd.)
-Hollow filler (D-2): Expanded, average particle size 60-90 μm
(Product name: Expandel 920 DE 80 d30, manufactured by Nippon Phillight Co., Ltd.)
Hollow filler (D-3): unexpanded, average particle size 10-16 μm (when heated at 80 ° C., the average particle size becomes 35-50 μm)
(Product name: Expandel 031 DU 40, manufactured by Nippon Phillight Co., Ltd.)

Isocyanate group-containing compound (E)
-Isocyanate group-containing compound (E-1)
Isocyanurate modified product of hexamethylene diisocyanate (trade name: Duranate TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.)
-Isocyanate group-containing compound (E-2): Crude MDI
(Product name: Luplanate M5S, manufactured by BASF INOAC Polyurethane)

Table 1 shows the materials used for forming the polyurethane resin compositions of Examples 1 to 19 and Comparative Examples 1 and 2, the blending amounts thereof (numerical values are parts by mass), the proportions of some of the materials, and the following. The result of each evaluation is shown.

(Manufacturing of polyurethane resin composition)
A polyol composition is produced by mixing a mixture of materials excluding the isocyanate group-containing compound (E) for 30 minutes using Disper (manufactured by Primix Corporation, model name: TK homodisper 2.5 type). Then, the isocyanate group-containing compound (E) is added to the polyol composition so that NCO / OH = 1 to 1.1, mixed and defoamed, and allowed to stand in an environment of 80 ° C. for 16 hours. To produce a polyurethane resin composition. Using the polyurethane resin composition thus produced, the density, dielectric constant, flame retardancy, insulating property, and density difference in the polyurethane resin composition are evaluated as described later.

Here, the produced polyurethane resin composition has a polyurethane resin (X) produced by the reaction of the hydroxyl group-containing compound (A) and the isocyanate group-containing compound (E), an inorganic filler (C), and a hollow portion inside. It contains a hollow filler (D) having and having a resin outer shell.

Further, the produced polyol composition is a composition (Y) capable of producing a polyurethane resin composition by mixing with another material, that is, an isocyanate group-containing compound (E), and has an inorganic filler (C) and an inside. It is a resin production composition (Y) containing a hollow filler (D) having a hollow portion and a resin outer shell.

(density)
As an evaluation of the weight of the polyurethane resin composition, the density of the polyurethane resin composition is measured. Density is measured according to JIS K0061 (balance method). However, a sample of 3 cm × 3 cm × 1 cm is used for the measurement. The sample is a polyurethane resin composition produced by using a container having a bottom of 3 cm × 3 cm and having a height of 1 cm.
The evaluation criteria are shown below.
◯: 1.2 g / cm less than ³ Δ: 1.2 g / cm ³ or more 1.5 g / cm less than ³ ×: 1.5 g / cm ³ or more

(Dielectric constant)
Using an Agilent Technologies LCR meter E4980A and a test fixture 16451B, the relative permittivity (1 MHz) is measured in an environment of 25 ± 5 ° C. and 65 ± 5% RH. A 6 cm × 6 cm × 0.3 cm sample is used for the measurement. The sample is a polyurethane resin composition produced by using a container having a bottom of 6 cm × 6 cm and having a height of 0.3 cm.
The evaluation criteria are shown below.
◯: Less than 4.0 Δ: 4.0 or more and less than 5.0 ×: 5.0 or more

(Flame retardance)
Flame retardancy is measured according to UL 94 of UL standard. The evaluation criteria are shown below.
◯: Equivalent to V-0 Δ: Equivalent to V-1 ×: V-2 or less

(Insulation)
The volume resistivity value is measured according to JIS K6911. The evaluation criteria are shown below.
○: 1 × 10 ¹² Ω ・ cm or more ×: 1 × 10 ¹² Ω ・ cm

(Density difference)
After mixing the above-mentioned polyol composition and the above-mentioned isocyanate group-containing compound (E), the mixture is poured into a container having a bottom of 3 cm × 3 cm so that the height of the completed polyurethane resin composition is 10 cm, and polyurethane is used. Complete the resin composition. The upper part (hereinafter, also referred to as the upper part of the resin) and the lower part (hereinafter, also referred to as the lower part of the resin) of the completed polyurethane resin composition are cut out, and the difference in density between the upper part of the resin and the lower part of the resin is compared. The upper part of the resin is a portion 1 cm from the upper end of the polyurethane resin composition of 3 cm (length) × 3 cm (width) × 10 cm (height). The lower portion of the resin is a portion of the polyurethane resin composition 1 cm from the lower end. Density measurement follows JIS K0061 (balance method). The evaluation criteria are shown below.
◯: Density difference is less than 10% ×: Density difference is 10% or more

In each example, a polyol composition is produced, and then an isocyanate group-containing compound (E) is added to the polyol composition to produce a polyurethane resin composition, but the method for producing the polyurethane resin composition is limited to this. It's not a thing. In Example 18, as the unexpanded hollow filler (D), a hollow filler (D) having a diameter of 35 μm to 50 μm when heated at 80 ° C. was used, but the average particle size was 30 μm when heated. The same effect can be obtained by using another hollow filler (D) as long as it is a hollow filler having a diameter of about 100 μm.

As can be seen from Examples 1 to 19 in Table 1, the density, dielectric constant and difficulty of the polyurethane resin composition by containing the polyurethane resin (X), the inorganic filler (C) and the hollow filler (D). Good flammability. Further, as can be seen from the comparison between Example 19 and other examples, by adjusting the blending amounts of the inorganic filler (C) and the hollow filler (D), the flame retardancy and the insulating property are improved, and the polyurethane resin is obtained. The density difference in the composition can be reduced. In Comparative Example 1, since the hollow filler (D) is not blended, the density has increased. In Comparative Example 2, since the amount of the inorganic filler (C) blended is small and the hollow filler (D) is not blended, the flame retardancy is low and the density is slightly high.

Here, the polyurethane resin composition has been described. Next, other resin compositions will be briefly described.

[Second Embodiment]
In the second embodiment, the silicone resin composition will be described as another example of the resin composition according to the present invention. The silicone resin composition in the present embodiment contains a silicone resin (X), an inorganic filler (C), and a hollow filler (D).

In the case of the silicone resin composition as well, by blending the inorganic filler (C) and the hollow filler (D) in the same manner as the polyurethane resin composition, the weight of the entire resin composition can be increased while increasing the flame retardancy of the resin composition. It can be suppressed and the dielectric constant can be further suppressed.

<Example>
Hereinafter, the silicone resin composition of the present embodiment will be described based on Examples and Comparative Examples. The present invention is not limited thereto. In addition, "part" and "%" in this specification represent "part by mass" and "% by mass", respectively, unless otherwise specified.

The materials used in Examples and Comparative Examples are shown.
Organopolysiloxane (P): Dimethylpolysiloxane with both ends of the molecular chain dimethylvinylsilyl group sealed

Plasticizer (B): Methyl oil

Inorganic filler (C)
-Inorganic filler (C-1): Aluminum hydroxide (trade name: C-305, manufactured by Sumitomo Chemical Co., Ltd.)
-Inorganic filler (C-2): Magnesium hydroxide
(Product name: ECOMAG, Tateho Chemical Industries, Ltd.)

Hollow filler (D)
-Hollow filler (D-1): Expanded, average particle size 33-55 μm
(Product name: Expandel 920 DE 40 d30, manufactured by Nippon Phillight Co., Ltd.)
-Hollow filler (D-2): Expanded, average particle size 60-90 μm
(Product name: Expandel 920 DE 80 d30, manufactured by Nippon Phillight Co., Ltd.)
Hollow filler (D-3): unexpanded, average particle size 10-16 μm (35-50 μm when heated at 80 ° C)
(Product name: Expandel 031 DU 40, manufactured by Nippon Phillight Co., Ltd.)

Catalyst (Q): Platinum group metal catalyst

Organohydrogen Polysiloxane (R)
-Organohydrogenpolysiloxane (R-1): Hexadecamethylpentadecane octasiloxane-Organohydrogenpolysiloxane (R-2): Methylhydrogenpolysiloxane

Table 2 shows the materials used for forming the Si-lagoon resin compositions of Examples 1 to 15 and Comparative Examples 1 and 2, and the blending amounts thereof (numerical values are parts by mass) and a part thereof. The ratio of the material of the above and the result of each evaluation described later are shown.

(Manufacturing of silicone resin composition)
The composition (Y) is prepared by mixing a mixture of materials excluding organohydrogenpolysiloxane (R) for 30 minutes using Disper (manufactured by Primix Corporation, model name: TK Homo Disper 2.5 type). Manufactured. Then, organohydrogenpolysiloxane (R) was added to the composition (Y), mixed and defoamed, and allowed to stand in an environment of 80 ° C. for 16 hours to produce a silicone resin composition. Using the silicone resin composition thus produced, the density, dielectric constant, flame retardancy, insulating property, and density difference in the silicone resin composition were evaluated as described later.

Here, the produced silicone resin composition contains a silicone resin (X) produced by the reaction of an organopolysiloxane (P) and an organohydrogenpolysiloxane (R), an inorganic filler (C), and a hollow portion inside. And contains a hollow filler (D) having a resin outer shell.

Further, the produced composition (Y) can produce a resin composition by mixing with another material, that is, organohydrogenpolysiloxane (R), and has an inorganic filler (C) and a hollow portion inside. It is a composition for resin production containing a hollow filler (D) having and having a resin outer shell.

(density)
The density of the silicone resin composition is measured according to JIS K0061 (balance method). A sample of 3 cm × 3 cm × 1 cm is used for the measurement. The sample is a silicone resin composition produced so as to have a height of 1 cm using a container having a bottom of 3 cm × 3 cm. The evaluation criteria are shown below.
◯: 1.2 g / cm less than ³ Δ: 1.2 g / cm ³ or more 1.5 g / cm less than ³ ×: 1.5 g / cm ³ or more

(Dielectric constant)
Using an Agilent Technologies LCR meter E4980A and a test fixture 16451B, the relative permittivity (1 MHz) is measured in an environment of 25 ± 5 ° C. and 65 ± 5% RH. A 6 cm × 6 cm × 0.3 cm sample is used for the measurement. The sample is a silicone resin composition produced by using a container having a bottom of 6 cm × 6 cm and having a height of 0.3 cm. The evaluation criteria are shown below.
◯: Less than 4.0 Δ: 4.0 or more and less than 5.0 ×: 5.0 or more

(Flame retardance)
Flame retardancy is measured according to UL 94 of UL standard. The evaluation criteria are shown below.
◯: Equivalent to V-0 Δ: Equivalent to V-1 ×: V-2 or less

(Insulation)
The volume resistivity value is measured according to JIS K6911. The evaluation criteria are shown below.
◯: 10 ¹² Ω ・ cm or more ×: 10 ¹² Ω ・ cm or less

(Density difference)
After mixing the above composition (Y) and organohydrogenpolysiloxane (R), it is poured into a container having a bottom of 3 cm × 3 cm so that the height of the completed silicone resin composition is 10 cm. Complete the silicone resin composition. The upper part (hereinafter, also referred to as the upper part of the resin) and the lower part (hereinafter, also referred to as the lower part of the resin) of the completed silicone resin composition are cut out, and the difference in density between the upper part of the resin and the lower part of the resin is compared. The upper part of the resin is a portion 1 cm from the upper end of the silicone resin composition of 3 cm (length) × 3 cm (width) × 10 cm (height). The lower portion of the resin is a portion of the silicone resin composition 1 cm from the lower end. Density measurement follows JIS K0061 (balance method). The evaluation criteria are shown below.
◯: Density difference is less than 10% ×: Density difference is 10% or more

In each embodiment, the composition (Y) was produced, and then organohydrogenpolysiloxane (R) was added to the composition (Y) to produce a silicone resin composition, wherein the silicone resin composition was produced. The method is not limited to this.

As can be seen from Examples 1 to 15 in Table 2, the density, dielectric constant and difficulty of the silicone resin composition by containing the silicone resin (X), the inorganic filler (C) and the hollow filler (D). Good flammability. Further, as can be seen from the comparison between Example 15 and other examples, by adjusting the blending amounts of the inorganic filler (C) and the hollow filler (D), the flame retardancy and the insulating property are improved, and the silicone resin. The density difference in the composition can be reduced.

Here, the silicone resin composition has been described. Next, other resin compositions will be briefly described.

[Third Embodiment]
In the third embodiment, the epoxy resin composition will be described as another example of the resin composition according to the present invention. The epoxy resin composition in the present embodiment contains an epoxy resin (X), an inorganic filler (C), and a hollow filler (D).

In the case of the epoxy resin composition as well as the polyurethane resin composition, by blending the inorganic filler (C) and the hollow filler (D), the weight of the entire resin composition can be increased while increasing the flame retardancy of the resin composition. It can be suppressed and the dielectric constant can be further suppressed.

<Example>
Hereinafter, the epoxy resin composition of the present embodiment will be described based on Examples and Comparative Examples. The present invention is not limited thereto. In addition, "part" and "%" in this specification represent "part by mass" and "% by mass", respectively, unless otherwise specified.

The epoxy resin is a thermosetting resin that can be cured by forming a cross-linked network with the epoxy groups remaining in the polymer. An epoxy resin is produced by mixing a prepolymer (S) before cross-linking networking and a curing agent (T) and performing a thermosetting treatment. The materials used in Examples and Comparative Examples are shown.

Prepolymer (S)
-Prepolymer (S-1): Biphenyl type epoxy resin (trade name: NC-3000SH, manufactured by Nippon Kayaku Co., Ltd.)
-Prepolymer (S-2): Bisphenol A type epoxy resin (trade name: EPICLON850, manufactured by DIC Corporation)

Inorganic filler (C)
-Inorganic filler (C-1): Aluminum hydroxide (trade name: C-305, manufactured by Sumitomo Chemical Co., Ltd.)
-Inorganic filler (C-2): Magnesium hydroxide
(Product name: ECOMAG, Tateho Chemical Industries, Ltd.)

Hollow filler (D)
-Hollow filler (D-1): Expanded, average particle size 33-55 μm
(Product name: Expandel 920 DE 40 d30, manufactured by Nippon Phillight Co., Ltd.)
-Hollow filler (D-2): Expanded, average particle size 60-90 μm
(Product name: Expandel 920 DE 80 d30, manufactured by Nippon Phillight Co., Ltd.)
Hollow filler (D-3): unexpanded, average particle size 10-16 μm (when heated at 80 ° C., the average particle size becomes 35-50 μm)
(Product name: Expandel 031 DU 40, manufactured by Nippon Phillight Co., Ltd.)

Catalyst (Q)
(Product name: DBU (1,8-diazabicyclo (5.4.0) Undesen-7), manufactured by San Apro)

Hardener (T)
-Curing agent (T-1): Phenol resin-based curing agent (trade name: phenol novolac resin HF series, manufactured by Meiwa Kasei Co., Ltd.)
-Curing agent (T-2): Acid anhydride compound

Table 3 shows the materials used for forming the epoxy resin compositions of Examples 1 to 16 and Comparative Examples 1 to 3, their blending amounts (parts by mass), the proportions of some of the materials, and each described later. The result of the evaluation is shown.

(Manufacturing of epoxy resin composition)
The composition (Y) is produced by mixing a mixture of materials excluding the curing agent (F). Then, the curing agent (F) is added to the composition (Y), mixed and defoamed, pre-cured at 130 ° C. for 60 minutes, and post-cured at 180 ° C. for 60 minutes to obtain an epoxy resin composition. To manufacture. Using the epoxy resin composition thus produced, the density, dielectric constant, flame retardancy, insulating property, and density difference in the epoxy resin composition are evaluated as described later.

Here, the produced epoxy resin composition has an epoxy resin (X) produced by the reaction of the prepolymer (S) and the curing agent (T), an inorganic filler (C), and a hollow portion inside. It also contains a hollow filler (D) having a resin outer shell.

Further, the produced composition (Y) can produce a resin composition by mixing with another material, that is, a curing agent (T), and has an inorganic filler (C) and a hollow portion inside. Moreover, it is a composition for resin production containing a hollow filler (D) having a resin outer shell.

(density)
The density of the epoxy resin composition is measured according to JIS K0061 (balance method). A sample of 3 cm × 3 cm × 1 cm is used for the measurement. The sample is an epoxy resin composition produced by using a container having a bottom of 3 cm × 3 cm and having a height of 1 cm. The evaluation criteria are shown below.
◯: 1.2 g / cm less than ³ Δ: 1.2 g / cm ³ or more 1.5 g / cm less than ³ ×: 1.5 g / cm ³ or more

(Dielectric constant)
Using an Agilent Technologies LCR meter E4980A and a test fixture 16451B, the relative permittivity (1 MHz) is measured in an environment of 25 ± 5 ° C. and 65 ± 5% RH. A 6 cm × 6 cm × 0.3 cm sample is used for the measurement. The sample is an epoxy resin composition produced by using a container having a bottom of 3 cm × 3 cm and having a height of 0.3 cm. The evaluation criteria are shown below.
◯: Less than 4.0 Δ: 4.0 or more and less than 5.0 ×: 5.0 or more

(Flame retardance)
Flame retardancy is measured according to UL 94 of UL standard. The evaluation criteria are shown below.
◯: Equivalent to V-0 Δ: Equivalent to V-1 ×: V-2 or less

(Insulation)
The volume resistivity value is measured according to JIS K6911. The evaluation criteria are shown below.
The evaluation criteria are shown below.
◯: 10 ¹² Ω ・ cm or more ×: 10 ¹² Ω ・ cm or less (density difference)
After mixing the above composition (Y) and the curing agent (T), the epoxy resin composition is poured into a container having a bottom of 3 cm × 3 cm so that the height of the finished epoxy resin composition is 10 cm. Complete the thing. The upper part (hereinafter, also referred to as the upper part of the resin) and the lower part (hereinafter, also referred to as the lower part of the resin) of the completed epoxy resin composition are cut out, and the difference in density between the upper part of the resin and the lower part of the resin is compared. The upper part of the resin is a portion 1 cm from the upper end of the epoxy resin composition of 3 cm (length) × 3 cm (width) × 10 cm (height). The lower portion of the resin is a portion of the polyurethane resin (X) 1 cm from the lower end. The measurement follows JIS K0061 (balance method). The evaluation criteria are shown below.

In the present embodiment, the composition (Y) is produced, and then the curing agent (F) is added to the composition (Y) to produce an epoxy resin composition. It is not limited to.

As can be seen from Examples 1 to 17 in Table 3, the density, dielectric constant and difficulty of the epoxy resin composition by containing the epoxy resin (X), the inorganic filler (C) and the hollow filler (D). Good flammability. Further, as can be seen from the comparison between Example 17 and other examples, by adjusting the blending amount of the hollow filler (D), the flame retardancy and the insulating property are improved, and the density difference in the epoxy resin composition is improved. Can be made smaller.

Similar effects can be obtained for other resin compositions not described in the present disclosure by blending the inorganic filler (C) and the hollow filler (D).

Claims (7)

With resin (X),
Inorganic filler (C) and
A resin composition comprising a hollow filler (D) having a hollow portion inside and a resin outer shell.
The resin (X) is a polyurethane resin produced by the reaction of the hydroxyl group-containing compound (A) and the isocyanate group-containing compound (E).
The hydroxyl group-containing compound (A) contains one or more selected from castor oil-based polyols and polybutadiene polyols.
The inorganic filler (C) is one or more selected from aluminum hydroxide and magnesium hydroxide.
The inorganic filler (C) is contained in an amount of 45 to 70 parts by mass with respect to 100 parts by mass of the resin composition, and the hollow filler (D) is contained in an amount of 0.5 to 5 parts by mass with respect to 100 parts by mass of the resin composition. Resin composition. The resin composition according to claim 1, wherein the hollow filler (D) has an average particle size of 30 μm to 100 μm. The resin composition according to claim 1 or 2, which is used for sealing an electric / electronic component. An electrical and electronic component sealed by the resin composition according to claim 3. A composition (Y) capable of producing a resin composition by mixing with another material , an isocyanate group-containing compound (E) .
Inorganic filler (C) and
A resin-producing composition (Y) comprising a hollow filler (D) having a hollow portion inside and a resin outer shell.
The composition (Y) contains a hydroxyl group-containing compound (A) , and the composition (Y) contains a hydroxyl group-containing compound (A).
The hydroxyl group-containing compound (A) contains one or more selected from castor oil-based polyols and polybutadiene polyols.
The inorganic filler (C) is one or more selected from aluminum hydroxide and magnesium hydroxide.
The inorganic filler (C) is contained in an amount of 50 to 80 parts by mass based on 100 parts by mass of the resin-producing composition.
The hollow filler (D) is contained in an amount of 1 to 5 parts by mass with respect to 100 parts by mass of the resin-producing composition.
Composition for resin production. The composition for resin production according to claim 5, wherein the hollow filler (D) has an average particle size of 30 μm to 100 μm. The composition for resin production according to claim 5 or 6, wherein the hollow filler (D) has thermal expansion properties.