KR20160145532A - Polyol composition for producing polyurethane resin composition - Google Patents

Abstract

A polyurethane resin composition containing an inorganic filler and further suppressed foaming.
A polyurethane resin composition is prepared by using a polyol composition for a polyurethane resin composition, which comprises a polyol, an inorganic filler and a catalyst, the water content of which is adjusted to 0.2% or less by a warming treatment and / .

Description

[0001] POLYOL COMPOSITION FOR PRODUCING POLYURETHANE RESIN COMPOSITION [0002]

The present invention relates to a polyol composition for the production of a polyurethane resin composition, a polyurethane resin composition containing the polyol composition, and electric and electronic parts sealed with the resin composition.

2. Description of the Related Art In recent years, electric and electronic components have become more densified and highly integrated, and the demand for reliability improvement of each component has become stronger. In such a situation, the influence of external environmental factors (physical factors such as vibration and drop, ultraviolet rays, chemical factors such as moisture and salinity) to electrical and electronic parts by sealing electrical and electronic parts such as printed boards with resin An attempt is being made to resolve it. For example, a polyurethane resin is used as an electrical insulating sealing material for electrical and electronic parts because of its good flexibility, abrasion resistance, low temperature curability, electrical characteristics and the like.

In addition, polyurethane resins are widely used as coatings, adhesives, and the like in a wide range of fields such as electric, electronic, automobile, civil engineering, and construction besides electric insulating sealing materials.

Patent Document 1: JP-A-2010-150474 Disclosure Patent Document 2: JP-A-2010-180384 Patent Document 3: JP 2000-219806 A Patent Document 4: Japanese Patent Application Laid-Open No. 2005-132093

When producing a polyurethane resin for use in electric and electronic parts, an inorganic filler represented by a metal hydroxide may be blended for the purpose of imparting heat and flame retardancy. In this case, however, the blending ratio of the polyol and the polyisocyanate becomes small, so that it is considered that the foaming and the defective curing tend to occur even in the presence of a very small amount of water. In a polyurethane resin, foaming is not preferable when it is used as an electrically insulating sealing material because it leads to deterioration of waterproofness, electrical insulation, and further, heat dissipation.

In Patent Document 1, the problem of hardening defects is solved by using metal hydroxides having specific physical properties, but other inorganic fillers can not be handled. Patent Documents 2 to 4 disclose techniques for dehydration of polyols (Patent Document 2: dehydrating agent, Patent Documents 3 and 4: thermal decompression). However, these methods are not limited to the above- The problem is not considered. Further, Patent Documents 1 to 4 have not been examined from the viewpoint of suppressing foaming.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a polyurethane resin composition containing an inorganic filler and further suppressed foaming. Further, there is also an object to provide a polyurethane resin composition excellent in thermal conductivity and also excellent in stability of curing (moderate curing rate, hardly causing foaming or hardening failure, and having little change in curing rate).

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have found that a polyurethane resin composition comprising a polyol, an inorganic filler and a catalyst and having a moisture content adjusted to 0.2% or less by a warming treatment and / It has been found that the above object can be achieved by producing a polyurethane resin composition using a polyol composition for production (hereinafter abbreviated as "the polyol composition of the present invention"). The present invention has been accomplished by carrying out further research based on this finding. That is, the present invention includes the following embodiments.

Item 1. A polyol composition for producing a polyurethane resin composition, which contains a polyol, an inorganic filler and a polymerization catalyst, the water content of which is adjusted to 0.2% or less by a warming treatment and / or a decompression treatment.

Item 2. The polyol composition according to Item 1, wherein the inorganic filler is a metal hydroxide.

Item 3. The polyol composition according to Item 1 or 2, wherein the content of the inorganic filler is 50 to 85 mass% with respect to 100 mass% of the polyol composition.

Item 4. The polyol composition according to any one of Items 1 to 3, wherein the polyol is a polybutadiene polyol and / or a castor oil-based polyol.

Item 5. (Process a) A step of reducing the water content of the composition by heating and / or pressure-reducing the composition containing the polyol and the inorganic filler,

(Step b) A step of adding a polymerization catalyst to the composition through Step a,

(Step c) A step of lowering the water content of the composition by heating and / or pressure-reducing the composition through Step b

Wherein the polyol composition is a polyol composition according to any one of < RTI ID = 0.0 > 1 to 4. < / RTI >

Item 6. The method according to item 6, wherein the temperature condition of the heating treatment in the step a is 40 占 폚 to 130 占 폚,

The temperature condition of the heating treatment in the step c is 40 占 폚 to 70 占 폚,

The polyol composition according to item 5, wherein the atmospheric pressure condition of the pressure reduction treatment in steps a and c is 2.7 kPa or less.

Item 7. The polyol composition according to any one of Items 1 to 6, which is used for producing a polyurethane resin composition for sealing electric and electronic parts.

Item 8. A polyurethane resin composition comprising a polyisocyanate and the polyol composition described in any one of Items 1 to 7.

Item 9. An electric / electronic part which is resin-sealed with the polyurethane resin composition according to item 8.

Item 10. The use of the polyol composition for the production of the polyurethane resin composition, which comprises a polyol, an inorganic filler and a polymerization catalyst, the water content of which is adjusted to 0.2% or less by a warming treatment and / or a decompression treatment.

Item 11. The use according to Item 10 for the production of a polyurethane resin composition for sealing electric and electronic parts.

Item 12. (Process a) A step of reducing the water content of the composition by heating and / or pressure-reducing the composition containing the polyol and the inorganic filler,

(Step b) A step of adding a polymerization catalyst to the composition through Step a,

(Step c) A step of lowering the water content of the composition by heating and / or pressure-reducing the composition through Step b

≪ RTI ID = 0.0 > 1, < / RTI >

Item 13. The method according to item 13, wherein the temperature condition of the heating treatment in step a is 40 占 폚 to 130 占 폚,

The temperature condition of the heating treatment in the step c is 40 占 폚 to 70 占 폚,

The method according to item 12, wherein the atmospheric pressure condition of the pressure reduction process in the steps a and c is 2.7 kPa or less.

By preparing the polyurethane resin composition using the polyol composition of the present invention, a polyurethane resin composition (hereinafter referred to as "the polyurethane resin of the present invention ") having an inorganic filler and being more inhibited from foaming and excellent in thermal conductivity and hardening stability Quot; composition "in some cases). Since the polyurethane resin composition of the present invention has such properties, it is particularly suitable for sealing electric / electronic parts requiring waterproofness and heat radiation.

In this specification, the expression "containing" includes the notions of " comprising, "" consisting essentially of," The expression "hydrogen addition" means a hydrogen adduct.

1. Polyol composition

The polyol composition of the present invention is a polyol composition for producing a polyurethane resin composition, which contains a polyol, an inorganic filler and a catalyst, and has a moisture content adjusted to 0.2% or less by a warming treatment and / or a decompression treatment. Hereinafter, this will be described.

The polyol is not particularly limited as long as it is a polyol having two or more hydroxyl groups, and various polyols used in the polyurethane resin composition can be used. Examples of the polyol include polyhydric alcohols such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, But are not limited to, pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,2-hexanediol, 2,5-hexanediol, octanediol, nonanediol, decanediol, , Triethylene glycol, dipropylene glycol, cyclohexanediol, trimethylolpropane, glycerin, 2-methylpropane-1,2,3-triol, 1,2,6- hexanetriol, pentaerythritol, polylactone diol, Wherein the polyol is at least one selected from the group consisting of polylactone, polylactone, polylactone, polylactone triol, ester glycol, polyester polyol, polyether polyol, polycarbonate polyol, polybutadiene polyol, acryl polyol, silicone polyol, fluoropolyol, polytetramethyleneglycol, polypropylene glycol, Castor oil-based polyols, and dimeric acid-based polyols. Among these, it is preferable to use a castor oil-based polyol and / or a polybutadiene polyol.

The castor oil-based polyol is not particularly limited, and examples thereof include castor oil, castor oil derivative and the like.

The castor oil derivative is not particularly restricted but includes, for example, castor oil fatty acid; Hydrogenated castor oil hydrogenated with castor oil or castor oil fatty acid; Ester exchanges of castor oil and other oils; Reactants of castor oil and polyhydric alcohols; An esterification reaction product of a castor oil fatty acid and a polyhydric alcohol; And addition-polymerizing an alkylene oxide. Among the castor oil-based polyols, it is preferable to use castor oil.

The molecular weight of the castor oil-based polyol is usually in the range of 100 to 4000, and preferably in the range of 300 to 2500.

The content of the hydroxyl group in the castor oil-based polyol is usually in the range of 30 to 500 mgKOH / g, preferably in the range of 100 to 200 mgKOH / g, as the hydroxyl value.

Examples of commercially available products that can be used as castor oil-based polyols include URIC H-30 (hydroxyl value of 160, number of functional groups of 3) manufactured by Itosayu Corporation, Uric H-57 (hydroxyl value of 100, number of functional groups of 3) H-52 (having a hydroxyl value of 200 and a functional group number of 3).

The polybutadiene polyol is not particularly limited, but polybutadiene polyol may be used as long as it has a polybutadiene structure and two hydroxyl groups in the molecule. Among these, polybutadiene polyols preferably have hydroxyl groups at both ends of the chain-like polybutadiene structure. Examples of the polybutadiene polyol include poly (1,4-butadiene) polyol, poly (1,2-butadiene) polyol and poly (1,2- 1,4-butadiene) polyol. The poly (1, 2/1, 4-butadiene) polyol has repeating units composed of polybutadiene having 60 to 90 mol% of 1,4 bonds and 10 to 40 mol% of 1,2 bonds, Is 10 to 14, and a polyol having a hydroxyl group at both ends. That is, the polybutadiene polyol may have a polybutadiene structure in which 1, 3-butadiene bonds with trans 1 and 4, or may have a polybutadiene structure in which 1, 3-butadiene bonds with cis 1,4, -Butadiene having 1 or 2 bonded polybutadiene structures. It is also possible to have a polybutadiene structure in which these bonds are mixed.

The molecular weight of the polybutadiene polyol is preferably 800 to 4800, more preferably 1200 to 3000.

The polybutadiene polyol may be a hydrogenated polybutadiene polyol, and examples of the hydrogenated polybutadiene polyol include those disclosed in Japanese Patent Application Laid-Open No. 2-298574. The hydrogenated polybutadiene polyol is obtained by hydrogen addition of the polybutadiene polyol.

The polybutadiene polyol preferably has an average hydroxyl value of 20 to 250 mgKOH / g, more preferably 50 to 120 mgKOH / g, according to JIS K1557-1.

The number average molecular weight of the polybutadiene polyol (A2) is preferably 500 to 5000, and more preferably 1000 to 3500.

The number average molecular weight can be measured by gel permeation chromatography (GPC) (in terms of polystyrene). Specifically, the number average molecular weight by the GPC method was measured using Shodex GPC System 21 manufactured by Showa Denko K.K. as a measurement device and Shodex LF-804 / KF-803 / KF-804 manufactured by Showa Denko K.K as a mobile phase The column temperature can be measured using NMP at a temperature of 40 ° C and can be calculated using a calibration curve of standard polystyrene.

Examples of commercially available products that can be used as the non-hydrogenated polybutadiene polyol include polybutadiene diols (for example, Polybd (trademark) R-15HT, Poly bd (trademark) R-45HT (All manufactured by Idemitsu Kosan Co., Ltd.)), poly (1,2-butadiene) glycol (for example, G-1000, G-2000 and G-3000 (all manufactured by Nippon Soda Co., )). Examples of commercially available products that can be used as the hydrogenated polybutadiene diol include hydrogenated polybutadiene diols (for example, polytail H and polytail HA (all manufactured by Mitsubishi Chemical Corporation) having mainly repeating units of 1,4 bonds) , And hydrogenated polybutadiene diols (e.g., GI-1000, GI-2000, and GI-3000 (all trade names, manufactured by Nippon Soda Co., Ltd.) having mainly repeating units of 1 and 2 bonds. Of these commercial products, R-15HT and R-45HT are preferably used.

The polyols may be used singly or in combination of two or more.

The content of the polyol is not particularly limited, but is preferably 0.5 to 30 mass%, more preferably 1 to 25 mass%, based on 100 mass% of the polyol composition of the present invention.

The inorganic filler is not particularly limited, and various materials used in the polyurethane resin composition can be used. Examples of the inorganic filler include aluminum hydroxide, alumina, aluminum nitride, boron nitride, magnesium hydroxide, magnesium oxide, zeolite and the like. Of these, metal hydroxides are preferable from the viewpoint of excellent thermal conductivity and flame retardancy and suitable for sealing electric and electronic parts, and among the metal hydroxides, aluminum hydroxide, magnesium hydroxide and the like are more preferable Aluminum hydroxide.

The shape of the inorganic filler may be either spherical or irregular.

The inorganic fillers may be used alone or in combination of two or more.

The content of the inorganic filler is preferably 50 to 85% by mass, more preferably 55 to 85% by mass, based on 100% by mass of the polyol composition of the present invention, from the viewpoint of thermal conductivity and easiness of processing of the polyurethane resin composition finally obtained By mass, more preferably 60 to 80% by mass, and still more preferably 65 to 75% by mass.

The polymerization catalyst is not particularly limited, and any of those used in the polyurethane resin composition can be used. Examples of the polymerization catalyst include metal catalysts such as organotin catalysts, organic lead catalysts and organic bismuth catalysts, and amine catalysts. Examples of the organotin catalyst include dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin diacetate, and the like. Examples of the organic lead catalyst include lead octylate, lead octenate, and lead naphthenate. Examples of the organic bismuth catalyst include bismuth octylate and bismuth neodecanoate. Examples of the amine catalyst include diethylenetriamine, triethylamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N' Trimethylenediamine, dimethylaminoethanol, bis (2-dimethylaminoethyl) ether, and the like. As the polymerization catalyst, an organometallic compound, a metal complex compound or the like may be used.

The polymerization catalysts may be used alone or in combination of two or more.

The content of the polymerization catalyst is preferably 0.00001 to 10 mass%, more preferably 0.0001 to 5 mass%, based on 100 mass% of the polyol composition of the present invention.

In the polyol composition of the present invention, a plasticizer may be further added if necessary.

The plasticizer is not particularly limited, and various plasticizers which are used in the polyurethane resin composition can be used. Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, diisononyl phthalate and diundecyl phthalate; Adipic acid esters such as dioctyl adipate and diisononyl adipate; Castor oil esters such as methyl acetyl ricinolate, butyl acetyl ricinoleate, acetylated ricinoleic acid triglyceride, and acetylated polyricinol acid triglyceride; Trimellitic acid esters such as trioctyltrimellitate and triisononyl trimellitate; Pyromellitic acid esters such as tetraoctyl pyromellitate and tetraisononyl pyromellitate, and the like. Of these, diisononylphthalate is preferred.

The plasticizers may be used alone or in combination of two or more.

The content of the plasticizer is preferably 0.01 to 30% by mass, more preferably 1 to 20% by mass, based on 100% by mass of the polyol composition of the present invention. When the content of the plasticizer is within the above range, the heat resistance of the polyurethane resin composition is not significantly deteriorated, and the mixing viscosity at the time of producing the polyurethane resin composition can be lowered.

The polyurethane resin composition of the present invention may further contain additives such as a tackifier, a curing accelerator, a colorant, a chain extender, a crosslinking agent, a filler, a pigment, a filler, a flame retardant, an urethanation catalyst, an ultraviolet absorber, an antioxidant, A disinfectant, and a silane coupling agent.

The amount of these components to be used may be appropriately determined so as not to hinder the desired characteristics of the finally obtained polyurethane resin composition depending on the intended use.

The polyol composition of the present invention is characterized in that the water content is adjusted to 0.2% or less by the warming treatment and / or the pressure reduction treatment. By such preparation, foaming of the finally obtained polyurethane resin composition can be suppressed.

The method of measuring the water content is not particularly limited, and examples thereof include a capacity method and an all-volume method. Of these, the capacity method is preferable. The measuring device is not particularly limited, but a Karl Fischer moisture meter is preferable.

The lower limit of the water content is not particularly limited, but may be, for example, 0.01%.

The method of the warming treatment and / or the decompression treatment is not particularly limited as long as the method can adjust the water content to 0.2% or less. For example, a method including the following steps a to c can be mentioned.

(Process a) Process for reducing the water content of the composition by heating and / or pressure-reducing the composition containing the polyol and the inorganic filler

(Step b) A step of adding a polymerization catalyst to the composition through Step a

(Step c) A step of lowering the water content of the composition by heating and / or pressure-reducing the composition through Step b.

In the step a, "a composition containing a polyol and an inorganic filler" may contain other components such as a plasticizer and an additive, if necessary, as long as it does not contain a polymerization catalyst.

From the viewpoint of the effect of the present invention, the temperature condition of the heating treatment in the step a may be preferably 40 to 130 占 폚, more preferably 70 to 130 占 폚, and further preferably 90 to 130 占 폚 . It is also possible to suppress the volatilization of the plasticizer while removing water adsorbed to the inorganic filler in a short time by setting the temperature within such a range. From the viewpoint of the effect of the present invention, the atmospheric pressure condition of the pressure reduction treatment in Step a may be preferably 2.7 kPa or less, more preferably 2.0 kPa or less, and further preferably 1.5 kPa or less. By setting the pressure to such a range, it is possible to remove water and bubbles more efficiently, and further to shorten the defoaming time at the time of curing and the defoaming time at the time of use. In the step a, it is preferable to perform the heating treatment and the pressure reduction treatment at the same time.

The time for the warming treatment and / or the pressure reduction treatment in the step a may be, for example, about 0.25 to about 4 hours, preferably about 0.5 to about 2 hours, and more preferably about 0.75 to about 1.5 hours.

In the step b, other components such as a plasticizer and an additive may be added, if necessary, in addition to the polymerization catalyst.

From the viewpoint of the effect of the present invention, the temperature condition of the heating treatment in the step c may be preferably from 40 캜 to 70 캜, more preferably from 50 캜 to 70 캜. By setting the temperature within such a range, it is possible to suppress the volatilization of the catalyst while removing water in a short period of time. The atmospheric pressure condition of the pressure reduction treatment in Step a may be preferably 2.7 kPa or less, more preferably 2.0 kPa or less, and further preferably 1.5 kPa or less. In the step c, it is preferable that the heating treatment and the decompression treatment are simultaneously carried out.

The time for the warming treatment and / or the pressure reduction treatment in step c may be, for example, about 0.25 to about 4 hours, preferably about 0.5 to about 2 hours, and more preferably about 0.75 to about 1.5 hours.

The polyol composition of the present invention is used in the production of a polyurethane resin composition. The resulting polyurethane resin composition is particularly suitable for sealing electric / electronic parts because foaming is further suppressed and excellent in thermal conductivity and stability of curing.

2. Polyurethane resin composition

The polyurethane resin composition of the present invention contains a polyisocyanate and the polyol composition of the present invention.

The polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups, and various polyisocyanates which are used in the polyurethane resin composition can be used.

As the polyisocyanate, it is preferable to use an isocyanurate-modified product, and by using it, the heat resistance of the polyurethane resin composition is excellent.

Examples of such isocyanurate modified products include compounds modified with isocyanurate such as aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, and aromatic aliphatic polyisocyanate compounds.

Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine Isocyanate, 2-methylpentane-1, 5-diisocyanate, 3-methylpentane-1, 5-diisocyanate and the like.

Examples of the alicyclic polyisocyanate compound include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, and the like.

Examples of the aromatic polyisocyanate compound include tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4 , 4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.

Examples of the aromatic aliphatic polyisocyanate compound include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and?,?,? - tetramethylxylylene diisocyanate.

As the isocyanurate-modified product, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, or an isocyanurate-modified product of an aromatic polyisocyanate compound is preferable, and among these, hexamethylene diisocyanate or isocyanate of diphenylmethane diisocyanate The rate-modified product is more preferable.

Examples of the polyisocyanate include an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, an aromatic polyisocyanate compound, an aromatic aliphatic polyisocyanate compound and the like, in addition to the isocyanurate-modified product, and the allophanate- , A carbodiimide-modified product, an adduct-modified product, and the like. As the modifier thereof, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, or an isocyanurate-modified product of an aromatic polyisocyanate compound is preferable, and among these, hexamethylene diisocyanate or isocyanurate of diphenylmethane diisocyanate The rate-modified product is more preferable.

Examples of commercially available products of polyisocyanate include Millionate MTL (manufactured by Tosoh Corporation), Dyuranate TLA-100 (HDI isocyanurate manufactured by Asahi Kasei Chemicals Co., Ltd.), Coronate HX (HDI isocyanurate manufactured by Nippon Polyurethane Industry Co., Ltd.) .

The polyisocyanate may be used alone or in combination of two or more.

In the polyurethane resin composition of the present invention, the content of the polyisocyanate is not particularly limited, but is preferably from 1 to 50 mass%, more preferably from 5 to 40 mass%, based on 100 mass% of the polyol.

In the polyurethane resin composition of the present invention, the polyisocyanate and the polyol preferably have an NCO / OH ratio of 0.6 to 2.0, more preferably 0.7 to 1.5.

The method for producing the polyurethane resin composition of the present invention is not particularly limited and can be produced by a conventionally known method employed as a method for producing a polyurethane resin composition.

Such a production method includes, for example, a method comprising mixing an A agent comprising the polyol composition (made B) of the present invention and a polyisocyanate compound.

If the B contains a polyol, an inorganic filler and a polymerization catalyst, and the A contains a polyisocyanate, other components such as a plasticizer and an additive may be contained in either the A or B component.

The polyurethane resin composition may be a liquid before curing or may be cured. As a method of curing the polyurethane resin composition, a method of curing the polyurethane resin composition over time by mixing the A and B agents and reacting the polyol with the polyisocyanate can be mentioned. At this time, it may be heated. The heating temperature is preferably about 40 to 120 DEG C, and the heating time is preferably about 0.5 to 24 hours.

When the polyurethane resin composition of the present invention is a liquid before curing, its viscosity is preferably 600 Pa · s or less, more preferably 400 Pa · s or less. Particularly, it is preferable that the initial viscosity of the mixture (viscosity after 2 minutes from the start of mixing of the agent A and the agent B) is 100 Pa · s or less. By setting the viscosity to the above range, the polyurethane resin composition of the present invention can exhibit higher workability. In the present specification, the viscosity of the polyurethane resin composition before curing is a value measured by a Brookfield viscometer at 23 캜.

The polyurethane resin composition of the present invention can be used as a sealing material. The polyurethane resin composition is particularly suitable for sealing electric / electronic parts because foaming is more suppressed and heat conductivity and stability of curing are excellent. Examples of such electric and electronic parts include a transformer such as a transformer coil, a choke coil, and a reactor coil, an apparatus control base, and various sensors. Such electric / electronic parts are also one of the present invention. The electric and electronic parts of the present invention can be used in an electric washing machine, a toilet, a water heater, a water purifier, a bathroom, a dishwasher, a power tool, an automobile, a motorcycle,

(Example)

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited by these examples.

(1) Raw materials

<Polyisocyanate> MDI isocyanate (trade name: Millionate MTL, manufactured by TOSOH CORPORATION)

&Lt; Plasticizers &gt; Diisononyl phthalate (trade name: DINP, manufactured by J-PLUS)

Polyol 1 Polybutadiene polyol (trade name: R-15HT, product of Idemitsu Kosan Co., Ltd.) having an average hydroxyl value of 103 mg KOH / g,

&Lt; Polyol 2 &gt; Castor oil (trade name: castor oil, manufactured by Itosayu Corporation)

<Polyol 3> Polypropylene glycol (trade name: D-1000, manufactured by Mitsui Chemicals)

&Lt; Inorganic filler &gt; Aluminum hydroxide (trade name: H-32 (manufactured by Showa Denko)

<Polymerization Catalyst> Dibutyltin dilaurate (trade name: TN-12, manufactured by Sakai Chemical Industry Co., Ltd.).

(2) Preparation of B

(2-1) Examples 1 to 5 and Comparative Examples 1 to 4

A polyol, a plasticizer and an inorganic filler were charged into a reaction vessel and mixed at 2000 rpm for 3 minutes using a mixer (trade name: Awatoliren Taro, Shin-Kasei). The obtained composition was charged into a reactor, And dehydrated over 1 hour. The polymerization catalyst was added thereto, mixed, and dehydrated at 55-65 DEG C and 1.3 kPa or less for 1 hour. The obtained composition was made into a B solution. The water content of the product B was measured using a Karl Fischer moisture meter (MKA-610, manufactured by Kyoto Electronics Industry Co., Ltd.), a dehydrating solvent CM (manufactured by Mitsubishi Chemical Corporation, solvent) and a titration agent SS-Z (manufactured by Mitsubishi Chemical Corporation, The measurement results are as shown in Table 1.

(2-2) Examples 6 to 8

The same procedures as in Examples 1 to 5 and Comparative Examples 1 to 4 were carried out except that the polymerization catalyst was added at the same time when the polyol, the plasticizer and the inorganic filler were added to the mixer.

(3) Preparation of polyurethane resin composition

The agent A was added to the formulation B according to the formulation shown in Table 1, and the mixture was mixed at 2000 rpm for 60 seconds using a mixer (trade name: Awatolian Taro, manufactured by Singkis). The viscosity (mixed initial viscosity) at 23 캜 of the mixed solution two minutes after the start of the mixing was measured using a Brookfield viscometer (Table 1). The resulting mixture was used as a polyurethane resin composition. The equivalent number (NCO / OH) of the isocyanate group in the agent A to one equivalent of the active hydrogen (OH) in the agent B was set to "1.00" as shown in Table 1.

(4) Preparation of test piece

The prepared polyurethane resin composition was injected into a molding frame (130 x 60 x 20 mm). It was heated at 80 占 폚 for 16 hours, allowed to stand at room temperature for one day and cured to obtain a test piece.

(5) Evaluation test

The initial viscosity, foamability, hardness, thermal conductivity and curability of the mixture were evaluated according to the following methods and evaluation criteria. The evaluation results are shown in Table 1.

(5-1) Initial viscosity of the mixture

○: less than 600 Pa · s

×: 600 Pa · s or more

(5-2) Foaming

The presence or absence of foaming on the surface of the test piece was visually observed, and the foamability was evaluated according to the following evaluation criteria.

○: No foaming

B: Bubbles or cracks due to one or two foaming

X: With foam

(5-3) Hardness

The hardness of the test piece was measured using an Asuka rubber hardness tester type A manufactured by Polymer Co., and the hardness was evaluated according to the following evaluation criteria.

○: The measured value is less than A80

?: The measured value is A81 to 90

X: The measured value is A91 or higher

(5-4) Thermal conductivity

The thermal conductivity of the test piece was measured using QTM-500 manufactured by Kyoto Electronics Industry Co., Ltd., and the thermal conductivity was evaluated according to the following evaluation criteria.

?: Thermal conductivity of 0.5 W / m? K or more

X: Thermal conductivity is less than 0.5 W / m 占 K

(5-5) Curability

The viscosity of the polyurethane resin composition at 23 DEG C was measured with a BH rotational viscometer (manufactured by TOKI INDUSTRIAL CO., LTD.), And the time at which the viscosity became twice the initial viscosity of the mixture was defined as a pot life. Examples 6 to 8 show that the preparation of agent B has an increase in pot life of 10% or more as compared with the case of the same formulation as described in "(2-1) Examples 1 to 5 and Comparative Examples 1 to 4" Or less and 10% or more, respectively.

Claims (13)

A polyol, an inorganic filler and a polymerization catalyst, wherein the water content is adjusted to 0.2% or less by the warming treatment and / or the pressure reduction treatment
A polyol composition for producing a polyurethane resin composition.
The method according to claim 1,
Wherein the inorganic filler is a metal hydroxide
Polyol composition.
3. The method according to claim 1 or 2,
Wherein the content of the inorganic filler is 50 to 85% by mass with respect to 100% by mass of the polyol composition
Polyol composition.
4. The method according to any one of claims 1 to 3,
Wherein the polyol is a polybutadiene polyol and / or a castor oil-based polyol
Polyol composition.
5. The method according to any one of claims 1 to 4,
(Process a) A step of reducing the water content of the composition by heating and / or pressure-reducing the composition containing the polyol and the inorganic filler,
(Step b) A step of adding a polymerization catalyst to the composition through Step a,
(Step c) A step of lowering the water content of the composition by heating and / or pressure-reducing the composition through Step b
&Lt; RTI ID = 0.0 &gt;
Polyol composition.
6. The method of claim 5,
The temperature condition of the heating treatment in the step (a) is 40 ° C to 130 ° C,
The temperature condition of the heating treatment in the step c is 40 占 폚 to 70 占 폚,
When the atmospheric pressure condition of the pressure reduction process in the processes a and c is 2.7 kPa or less
Polyol composition.
7. The method according to any one of claims 1 to 6,
Phosphorus for the production of polyurethane resin compositions for electric and electronic parts encapsulation
Polyol composition.
A polyisocyanate composition comprising a polyisocyanate and a polyol composition according to any one of claims 1 to 7
Polyurethane resin composition.
The polyurethane resin composition according to claim 8,
Electric and electronic parts.
A polyol, an inorganic filler and a polymerization catalyst, wherein the water content is adjusted to 0.2% or less by the warming treatment and / or the pressure reduction treatment
Use of a polyol composition for the manufacture of a polyurethane resin composition.
11. The method of claim 10,
For the production of a polyurethane resin composition for sealing electrical and electronic parts
use.
(Process a) A step of reducing the water content of the composition by heating and / or pressure-reducing the composition containing the polyol and the inorganic filler,
(Step b) A step of adding a polymerization catalyst to the composition through Step a,
(Step c) A step of lowering the water content of the composition by heating and / or pressure-reducing the composition through Step b
A process for producing the polyol composition according to any one of claims 1 to 4,
Way.
13. The method of claim 12,
The temperature condition of the heating treatment in the step (a) is 40 ° C to 130 ° C,
The temperature condition of the heating treatment in the step c is 40 占 폚 to 70 占 폚,
When the atmospheric pressure condition of the pressure reduction process in the processes a and c is 2.7 kPa or less
Way.