JP2019099598A - Curable resin composition and electrical component using the same - Google Patents

Abstract

To provide a curable resin composition capable of giving a cured product having moist heat resistance, sufficient flexibility at a low temperature, and good initial strength, and to provide an electrical component using the same.SOLUTION: The curable resin composition contains a (meth)acrylic polyol and a urethane prepolymer. The (meth)acrylic polyol is composed of a polymer having a hydroxyl value of 5 mg KOH/g or more and 150 mg KOH/g or less, a glass transition temperature of -70°C or higher and -40°C or lower, and a number average molecular weight of 500 or more and 20,000 or less and being liquid at 25°C. The urethane prepolymer contains: a first structural unit derived from at least one polyol selected from the group consisting of a polycarbonate-based polyol, a castor oil-based polyol, and a hydrogenated polyolefin-based polyol; and a second structural unit derived from a polyisocyanate.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a curable resin composition and an electrical component using the same.

  Heretofore, curable resin compositions containing a polyol and a polyisocyanate are known. For example, Patent Document 1 is obtained by polymerizing a radically polymerizable monomer at a polymerization temperature of 150 to 350 ° C., a hydroxyl value of 5 to 55 mg KOH / g, a glass transition temperature of −70 to 10 ° C., and A curable resin composition for a sealing material is disclosed which comprises a copolymer having an average molecular weight of 500 to 20,000 and a polyoxyalkylene compound having two or more isocyanate groups at its terminal.

  Moreover, in Patent Document 2, an acrylic polyol and an isocyanate compound are contained, and the acrylic polyol is a polyol having a glass transition temperature of −20 to 20 ° C. obtained by polymerizing a polymerizable monomer, and the isocyanate compound is A curable resin composition is disclosed which comprises both an isocyanate having no aromatic ring and an isocyanate having an aromatic ring. The said curable resin composition is used for the adhesive agent for lamination sheets.

JP, 2001-40328, A JP, 2013-224374, A

  However, the cured product of the curable resin composition described in Patent Document 1 is degraded by hydrolysis or the like in a high-temperature, high-humidity environment as required for electrical components mounted in vehicles such as automobiles. It has no heat and moisture resistance.

  Moreover, the curable resin composition of patent document 2 is used for the adhesive agent for lamination sheets. Therefore, the glass transition temperature of the acrylic polyol is as high as -20 to 20 ° C. Therefore, since the cured product of this curable resin composition is inferior in flexibility in a low temperature environment required for a vehicle, high stress may be generated at the time of use at low temperature, which may cause cracking or peeling. is there. Moreover, when applying a hardened | cured material to the said electrically-wired part, it is also important that initial strength is favorable.

  The present invention has been made in view of such problems, and is a curable resin composition having moist-heat resistance, having sufficient flexibility at low temperatures, and capable of obtaining a cured product having good initial strength. An object of the present invention is to provide an electrical component using the same.

One embodiment of the present invention is a (meth) acrylic polyol.
And urethane prepolymer, and
The (meth) acrylic polyol is
A polymer having a hydroxyl value of 5 mgKOH / g or more and 150 mgKOH / g or less, a glass transition temperature of -70 ° C or more and -40 ° C or less, a number average molecular weight of 500 or more and 20000 or less, and liquid at 25 ° C;
The above urethane prepolymer is
A first structural unit derived from at least one polyol selected from the group consisting of a polycarbonate-based polyol, a castor oil-based polyol, and a hydrogenated polyolefin-based polyol, and a second structural unit derived from a polyisocyanate
It is in the curable resin composition.

  Another aspect of the present invention is an electrical component (1) having a sealing material (2) composed of a cured product of the curable resin composition.

Yet another aspect of the present invention comprises an adhesive layer bonding the case and the lid,
The said adhesive layer exists in the electrical component comprised from the hardened | cured material of the said curable resin composition.

  The curable resin composition forms a urethane bond by curing to form a polyurethane-based cured product. The cured product has moisture and heat resistance, has sufficient flexibility at low temperature, and has good initial strength, because the curable resin composition has the above-described configuration.

  Further, in the electric component having the sealing material constituted of the cured product of the curable resin composition, the sealing material has moisture and heat resistance, has sufficient flexibility at low temperature, and has good initial strength. Have. Therefore, this electric component is excellent in long-term insulation reliability, and can be suitably used for vehicles, such as a car.

  Further, in the above electric component having an adhesive layer composed of a cured product of the curable resin composition, the adhesive layer has moisture and heat resistance and heat resistance, has sufficient flexibility at low temperatures, and has good initial strength Have. Therefore, this electric component is excellent in long-term insulation reliability, and can be suitably used for vehicles, such as a car.

  The reference numerals in parentheses described in the claims and the means for solving the problems indicate the correspondence with the specific means described in the embodiments described later, and the technical scope of the present invention is limited. It is not a thing.

FIG. 5 is an overall cross-sectional view showing a schematic configuration of an electronic control unit as an example of an electrical component having a sealing material constituted of a cured product of a curable resin composition according to Embodiment 1.

(Embodiment 1)
The curable resin composition and the electric component of the first embodiment will be described with reference to FIG. As exemplified in FIG. 1, the electric component 1 of the present embodiment is, for example, an electronic control unit (that is, an ECU) for vehicle use, and the curable resin composition of the present embodiment is for the electric component 1. It is used as the sealing material 2. The electrical component 1 includes a case 11 made of resin, a substrate 3 housed in the case 11, and a sealing material 2. In addition, various electronic components (not shown) including an IC chip and a capacitor are mounted on the substrate 4. The sealing material 2 is made of a cured product in which the curable resin composition is injected into the case 11 and cured, and covers the entire substrate 3 including the electronic component.

  The substrate 3 is made of, for example, a known printed wiring board, and external connection terminals 41 and 42 are provided on the outer peripheral portion of the substrate 3 and penetrate the wall of the case 11 and extend to the outside. Although not illustrated in the present embodiment, for example, a cured product of a curable resin composition includes a case in which a substrate on which various electronic components are mounted is accommodated, a lid attached to the case, and a case and a lid It can also be used as an adhesive layer in an electronic component such as an electronic control unit having an adhesive layer for bonding.

  Here, the curable resin composition described above contains a (meth) acrylic polyol and a urethane prepolymer. Specifically, the curable resin composition can be of a two-component mixture type.

  In the curable resin composition, the term "(meth) acrylic" in the term "(meth) acrylic polyol" is meant to include not only acrylic but also methacrylic. Specifically, the (meth) acrylic polyol has a hydroxyl value of 5 mg KOH / g or more and 150 mg KOH / g or less, a glass transition temperature of -70 ° C. or more and -40 ° C. or less, and a number average molecular weight of 500 or more and 20000 or less, and 25 It is composed of a polymer which is liquid at ° C. In addition, not only a polymer but an oligomer is contained in the polymer said above. The polymer referred to above may be either a homopolymer or a copolymer. The polymer is preferably a copolymer from the viewpoint of easy control of physical properties of the cured product.

  In the (meth) acrylic polyol, when the hydroxyl value is less than 5 mg KOH / g, the curability may be reduced, and a cured product having poor moist heat resistance may be obtained. The hydroxyl value may be preferably 8 mg KOH / g or more, more preferably 12 mg KOH / g or more, and even more preferably 15 mg KOH / g or more from the viewpoint of securing moist heat resistance and the like. On the other hand, if the hydroxyl value exceeds 150 mg KOH / g, the cured product may become brittle due to excessive curing. The hydroxyl value can be preferably 145 mg KOH / g or less, more preferably 140 mg KOH / g or less, and even more preferably 135 mg KOH / g or less, from the viewpoint of securing flexibility at low temperature and the like. In addition, a hydroxyl value is a value measured based on JIS-K1557-1.

  In the (meth) acrylic polyol, the glass transition temperature is preferably as low as possible from the viewpoint of securing flexibility in a low temperature environment after curing. However, the glass transition temperature is set to −70 ° C. or more from the viewpoint of the availability of the (meth) acrylic polyol and the like. On the other hand, when the glass transition temperature exceeds -40 ° C., it becomes difficult to secure flexibility under low temperature environment required for vehicles, high stress occurs when used at low temperature, and cracks and peeling occur. There is a fear. The glass transition temperature is preferably −45 ° C. or less, more preferably −50 ° C. or less, and even more preferably −55 ° C. or less from the viewpoint of securing sufficient flexibility at a low temperature, etc. it can. In addition, the measuring method of a glass transition temperature is a value based on JISK7121 and is a value measured as an inflexion point of DSC.

  In a (meth) acrylic polyol, when the number average molecular weight is less than 500, the crosslink density of the cured product is increased and the elastic modulus of the cured product is increased, so the possibility of cracking or peeling in a cold environment is increased. . The number average molecular weight can be preferably 600 or more, more preferably 800 or more, and even more preferably 1000 or more from the viewpoint of suppressing an increase in the elastic modulus of the cured product. On the other hand, when the number average molecular weight exceeds 20000, there is a possibility that the workability of the curable resin composition may be lowered due to the increase in viscosity. The number average molecular weight can be preferably 18000 or less, more preferably 16000 or less, and even more preferably 14000 or less from the viewpoint of facilitating retention of the low viscosity of the curable resin composition. The number average molecular weight is a value measured by a GPC method (gel permeation chromatography method) using a solvent such as tetrahydrofuran (THF).

  The (meth) acrylic polyol is liquid at 25 ° C. When the (meth) acrylic polyol is solid at 25 ° C., it is necessary to dissolve it in a solvent or to liquefy it by heating when preparing the curable resin composition. On the other hand, if the (meth) acrylic polyol is liquid at 25 ° C., it is not necessary to dissolve it in a solvent at the time of preparation of the curable resin composition or to heat and liquefy it before mixing. The workability is good because it can be easily prepared.

  In the curable resin composition, the urethane prepolymer includes a first structural unit derived from at least one polyol selected from the group consisting of a polycarbonate-based polyol, a castor oil-based polyol, and a hydrogenated polyolefin-based polyol, and a polyisocyanate And a second structural unit derived from The urethane prepolymer may have an isocyanate group at at least one end, preferably from both the ends, from the viewpoint of, for example, improving the crosslinkability with the (meth) acrylic polyol. Specifically, such a urethane prepolymer can be composed of the reaction product of the above-mentioned polyol and polyisocyanate. The urethane prepolymer functions as a curing agent. When the curable resin composition contains the (meth) acrylic polyol and the urethane prepolymer, a cured product having a uniform crosslinked structure can be easily obtained.

  The polyol in the urethane prepolymer is preferably a polycarbonate-based polyol. According to this configuration, the heat resistance of the cured product can be improved.

  Specific examples of the polycarbonate-based polyol in the urethane prepolymer include polyols obtained by carbonate-modifying a single or a mixture of aliphatic diols such as hexanediol, pentanediol, butanediol and propanediol. These can be used alone or in combination of two or more. More specifically, examples of polycarbonate-based polyols include diols obtained by subjecting a mixture of hexanediol and pentanediol to carbonate modification and having hydroxyl groups at both ends.

  The polycarbonate-based polyol can have a hydroxyl value of 20 mg KOH / g or more and 300 mg KOH / g or less. According to this configuration, the viscosity at normal temperature is low, the workability is excellent, and a cured product having a high initial strength can be easily obtained. The hydroxyl value of the polycarbonate-based polyol is preferably 25 mg KOH / g or more and 280 mg KOH / g or less, more preferably 30 mg KOH / g or more and 260 mg KOH / g or less, and still more preferably 35 mg KOH / g from the viewpoint of adjusting physical properties of the cured product. It can be made into g or more and 250 mgKOH / g or less. In addition, the hydroxyl value of polycarbonate-type polyol is a value measured by JIS-K1557-1.

  Examples of the castor oil-based polyol in the urethane prepolymer include castor oil and castor oil derivatives. These can be used alone or in combination of two or more. Castor oil is mainly composed of an ester of a fatty acid consisting mainly of ricinoleic acid and glycerin, and has a hydroxyl group derived from ricinoleic acid and a double bond. Examples of the castor oil derivative include partially dehydrated condensates of castor oil, transesterified products of castor oil with low molecular weight polyols, polyether polyols or polyester polyols, or hydrogenated products thereof.

  The castor oil-based polyol may have an iodine value of 15 or less. According to this configuration, the oxidation reaction due to the double bond in the castor oil-based polyol decreases in a high temperature environment, and it becomes easy to suppress that the cured product becomes too hard with time. The iodine value can be preferably 13 or less, more preferably 12 or less, and even more preferably 10 or less. In addition, an iodine value is a value measured based on JISK 0070-1992.

  Examples of hydrogenated polyolefin-based polyols in urethane prepolymers include hydrogenated polyolefin-based polyols containing double bonds (C = C), polyolefin-based polyols not containing double bonds (C = C) in the main chain, etc. Be These can be used alone or in combination of two or more. In addition, the case where it is comprised so that a double bond may not be contained in a principal chain from the beginning besides the case where a double bond is made into a single bond by hydrogenation etc. is included also in said hydrogenation. Specific examples of the hydrogenated polyolefin-based polyol include hydrogenated polyolefin polyols such as hydrogenated (hydrogenated) polybutadiene and hydrogenated (hydrogenated) polyisoprene.

  The hydrogenated polyolefin-based polyol may have an iodine value of 15 or less. According to this configuration, the heat resistance of the cured product can be improved. The iodine value can be preferably 13 or less, more preferably 12 or less, and still more preferably 10 or less from the viewpoint of improving heat resistance and the like. In addition, an iodine value is a value measured based on JISK 0070-1992.

  The polyisocyanate in the urethane prepolymer may be an aliphatic polyisocyanate, an aromatic polyisocyanate, or both of them. According to the configuration in which the polyisocyanate in the urethane prepolymer contains an aliphatic polyisocyanate, the moist heat resistance of the cured product can be easily secured. Moreover, according to this configuration, there is also an advantage that it becomes easy to impart flexibility to the cured product. On the other hand, according to the configuration in which the polyisocyanate in the urethane prepolymer contains the aromatic polyisocyanate, the initial breaking strength and the adhesive strength of the cured product can be easily improved as compared with the aliphatic polyisocyanate.

  Specific examples of aliphatic polyisocyanates include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), derivatives thereof (modified products etc.) and the like. Among these, as aliphatic polyisocyanate, hexamethylene diisocyanate, and at least one of hexamethylene diisocyanate derivatives can be mentioned as suitable. As compared with isophorone diisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate derivatives have high reactivity because the number of substituents that cause steric hindrance around the isocyanate group which is a reaction point is small. Therefore, according to this configuration, it is possible to form a cured product in a shorter time. Moreover, according to this configuration, there is also an advantage that the curing temperature can be easily set lower.

  Specific examples of hexamethylene diisocyanate derivatives include biuret-modified hexamethylene diisocyanate, isocyanurate-modified hexamethylene diisocyanate, adduct-modified hexamethylene diisocyanate, prepolymer of hexamethylene diisocyanate, and the like. At least one selected from the group consisting of a mixture of and the like can be mentioned as suitable. According to this configuration, it is possible to obtain a cured product having moisture heat resistance, sufficient flexibility at low temperatures, and good initial strength. Moreover, according to this configuration, there is also an advantage that physical properties of the cured product can be easily controlled.

  Specific examples of the aromatic polyisocyanate include diphenylmethane diisocyanate (MDI) such as 2,2'-, 2,4'- or 4,4'-diphenylmethane diisocyanate, 2,2'-, 2,6. Examples thereof include '-toluene diisocyanate (TDI), derivatives thereof (modified products etc.) and the like. Among these, as the aromatic polyisocyanate, diphenylmethane diisocyanate, and at least one of diphenylmethane diisocyanate derivatives can be mentioned as preferable. According to this configuration, it is possible to react with the polyol with less heat to form a urethane prepolymer. Moreover, according to this configuration, there are also advantages such as the initial breaking strength of the cured product and the improvement of the adhesive strength.

  Specific examples of diphenylmethane diisocyanate derivatives include biuret-modified diphenylmethane diisocyanate, isocyanurate-modified diphenylmethane diisocyanate, adduct-modified diphenylmethane diisocyanate, prepolymer of diphenylmethane diisocyanate, and a mixture thereof At least one selected from the above and the like can be mentioned as suitable. According to this configuration, it is easier to adjust the initial breaking strength of the cured product. Moreover, according to this configuration, there is also an advantage that it is easy to further improve the breaking strength and the adhesive strength of the cured product.

  The polyisocyanate in the urethane prepolymer may be composed of a difunctional polyisocyanate or may be composed of a trifunctional polyisocyanate, or both of a bifunctional polyisocyanate and a trifunctional polyisocyanate. May be included. When the polyisocyanate contains both of difunctional polyisocyanate and trifunctional polyisocyanate, it becomes easy to adjust the hardness of the cured product.

  As other components in the curable resin composition, for example, at least one polyol selected from the group consisting of the polycarbonate-based polyol described above, a castor oil-based polyol, and a hydrogenated polyolefin-based polyol, the polyisocyanate described above, molecular weight Examples thereof include diols less than 300, plasticizers, catalysts, and additives added to a polyurethane-based curable resin composition. These can be used alone or in combination of two or more.

  When the curable resin composition further contains a polycarbonate-based polyol in addition to the (meth) acrylic polyol and the urethane prepolymer, the initial breaking strength of the cured product can be easily improved.

  When the curable resin composition further contains a castor oil-based polyol in addition to the (meth) acrylic polyol and the urethane prepolymer, the viscosity before curing is low and the castability is excellent.

  When the curable resin composition further contains a hydrogenated polyolefin polyol in addition to the (meth) acrylic polyol and the urethane prepolymer, the initial breaking strength of the cured product can be easily improved.

  When the curable resin composition further contains a polyisocyanate in addition to the (meth) acrylic polyol and the urethane prepolymer, the initial breaking strength of the cured product can be easily improved.

  When the curable resin composition further contains a diol having a molecular weight of less than 300 in addition to the (meth) acrylic polyol and the urethane prepolymer, the following advantages can be obtained. Diols having a molecular weight of less than 300 can function as diluents because they are small molecules. Therefore, in the above case, there is an advantage that it is easy to adjust the viscosity before the curable resin composition is cured. In addition, by containing a diol having a molecular weight of less than 300, there is also an advantage that during curing of the curable resin composition by crosslinking, the distance between crosslinking points becomes short, and the strength of the cured product can be easily improved. The molecular weight of the diol can be preferably 250 or less, more preferably 230 or less, and still more preferably 200 or less, from the viewpoint of improving the strength of the cured product and the like. The molecular weight of the diol can be preferably 60 or more from the viewpoint of suppressing volatilization at high temperatures. Specific examples of the diol having a molecular weight of less than 300 include octanediol, nonanediol, hexanediol, butanediol, ethylene glycol and the like.

  Specific examples of the plasticizer include phthalic acid esters such as dioctyl phthalate and dinonyl phthalate, adipic acid esters such as dioctyl adipate and dinonyl adipate, and tris (7-ethylhexyl trimellitate). Etc., phosphoric acid ester systems such as triethyl phosphate, etc. can be exemplified. Moreover, as a catalyst, an amine compound, a tin compound, a bismuth compound etc. can be illustrated specifically, for example.

  In the curable resin composition, the mass ratio of the (meth) acrylic polyol to the urethane prepolymer can be 60:40 to 30:70. According to this configuration, it is possible to obtain a cured product having moisture heat resistance, sufficient flexibility at low temperatures, and good initial strength. The mass ratio of the (meth) acrylic polyol to the urethane prepolymer is preferably 56:44 to 33:67, more preferably 53:47 to 35:65, still more preferably 50:50 to 37:63. It can be done.

  When the curable resin composition contains a polycarbonate-based polyol, the curable resin composition contains 3 to 50 parts by mass of the polycarbonate-based polyol per 100 parts by mass of the (meth) acrylic-based polyol and the urethane prepolymer in total. The following can be included. When the curable resin composition contains a castor oil-based polyol, the curable resin composition contains 3 parts by mass or more of the castor oil-based polyol per 100 parts by mass of the (meth) acrylic polyol and the urethane prepolymer in total. It can be contained in parts by mass or less. When the curable resin composition contains a hydrogenated polyolefin-based polyol, the curable resin composition contains 3 of the hydrogenated polyolefin-based polyol with respect to a total of 100 parts by mass of the (meth) acrylic polyol and the urethane prepolymer. It can contain 50 parts by mass or less.

  When the curable resin composition contains a polyisocyanate, the curable resin composition contains 1 part by mass or more and 20 parts by mass of polyisocyanate with respect to a total of 100 parts by mass of the (meth) acrylic polyol and the urethane prepolymer. The following can be included. In addition, when the curable resin composition contains a diol having a molecular weight of less than 300, the curable resin composition contains 0 diol having a molecular weight of less than 300 with respect to 100 parts by mass in total of the (meth) acrylic polyol and the urethane prepolymer. .5 parts by mass or more and 30 parts by mass or less can be included. When the curable resin composition contains a plasticizer, the curable resin composition contains 3 to 200 parts by mass of a plasticizer based on 100 parts by mass of the (meth) acrylic polyol and the urethane prepolymer in total. The following can be included. Moreover, when a curable resin composition contains a catalyst, the curable resin composition contains 0.0001 parts by mass or more and 5 parts by mass of a catalyst with respect to a total of 100 parts by mass of a (meth) acrylic polyol and a urethane prepolymer. The following can be included.

  By curing the above-mentioned curable resin composition, for example, by heating as necessary, a structural unit derived from the (meth) acrylic polyol and a structural unit derived from the urethane prepolymer can be obtained. It is possible to obtain a polyurethane-based cured product.

(Experimental example)
<Preparation of materials>
-(Meth) acrylic polyol-
-(Meth) acrylic polyol (1) (manufactured by Toagosei Co., Ltd., "ARUFON UH-2000", hydroxyl value: 20 mg KOH / g, glass transition temperature Tg: -60 ° C, number average molecular weight: about 4000, liquid at 25 ° C Polyacrylic polyol composed of a copolymer
・ (Meth) acrylic polyol (2) (synthesized product, hydroxyl value: 26 mg KOH / g, glass transition temperature Tg: 15 ° C., number average molecular weight: about 7000, copolymer composed of solid at 25 ° C. Poly acrylic polyol)
The (meth) acrylic polyol (2) was synthesized as follows. A flask was charged with 100 g of ethyl acetate (reagent) and 1 g of 2,2-azobisisobutyronitrile (AIBN) as a polymerization initiator, and the mixture was refluxed at 80 ° C. Next, 40 g of methyl methacrylate, 40 g of butyl acrylate, 10 g of acrylonitrile and 10 g of 2-hydroxyethyl methacrylate were slowly dropped, and after completion of the dropping, the mixture was heated and stirred for 4 hours to obtain a polyacrylic polyol having a solid content of 50%. Thereafter, the solvent ethyl acetate was removed under reduced pressure to obtain a solid polyacrylic polyol.

-Polyol-
・ Polycarbonate-based polyol (manufactured by Asahi Kasei Corp., "Duranol T5651", polycarbonate diol, hydroxyl value: 110 mg KOH / g, liquid)
-Castor oil based polyol (manufactured by Ito Oil Co., Ltd., "URIC PH-5001", hydroxyl value: 49 mg KOH / g, iodine value: 2)
-Hydrogenated polyolefin-based polyol (manufactured by Nippon Soda Co., Ltd., "GI-1000", hydrogenated polybutadiene having a hydroxyl group in the skeleton, iodine value: 10, hydroxyl value: 67 mg KOH / g)

-Urethane prepolymer-
· Urethane prepolymer (1) (synthetic product)
Polycarbonate-based polyol ("Duranol T5651", manufactured by Asahi Kasei Corp., polycarbonate diol, 110 mg KOH / g, liquid), and an aromatic polyisocyanate (manufactured by Tosoh Corp., "Millionate MTL", a carbodiimide modified product of diphenylmethane diisocyanate (MDI) ) At an equivalent ratio of NCO / OH = 2/1, and after addition of 20% by mass of a plasticizer (manufactured by J Plus, “TOTM”, tris (2-ethylhexyl) trimellitate) The mixture was heated and stirred at 70 ° C. for 12 hours. This obtained urethane prepolymer (1) of NCO% = 4.9%.
· Urethane prepolymer (2) (synthetic product)
In the synthesis of the urethane prepolymer (1), a castor oil-based polyol ("URIC PH-5001" manufactured by Ito Oil Co., Ltd., hydroxyl value: 49 mg KOH / g, iodine value: 2) was used in place of polycarbonate polyol. Similarly, an NCO% = 2.3% urethane prepolymer (2) was obtained.
· Urethane prepolymer (3) (synthetic product)
Hydrogenated polyolefin-based polyol (manufactured by Nippon Soda Co., Ltd., “GI-1000”, hydrogenated polybutadiene having a hydroxyl group in the skeleton, iodine value: 10, hydroxyl value: 67 mg KOH / g), aliphatic polyisocyanate (manufactured by Asahi Kasei Corporation, Duranate D101 ", a prepolymer body of hexamethylene diisocyanate (HDI) is mixed at an equivalent ratio of NCO / OH = 2/1, and a plasticizer (manufactured by J Plus Co.," TOTM ", trimellitic acid tris After adding (2-ethylhexyl) for 20 mass%, it heat-stirred at 70 degreeC for 12 hours. This gave a urethane prepolymer (3) with NCO% = 2.9%.

-Polyisocyanate-
Aliphatic polyisocyanate (bifunctional) (manufactured by Asahi Kasei Corp., "Duranate D101", prepolymer of hexamethylene diisocyanate (HDI), NCO%: 19.6)
· Aromatic polyisocyanate (trifunctional) (Tosoh Co., Ltd., "Millionate MR-200", oligomer of diphenylmethane diisocyanate (MDI), NCO%: 31.2)

・ Plasticizer (manufactured by J Plus Co., "TOTM", tris trimellitate (2-ethylhexyl))
・ Catalyst (Nitto Kasei Co., Ltd., “Neostan U600”, bismuth-based compound)

<Preparation of sample>
As shown in Tables 1 and 2 described later, a (meth) acrylic polyol, if necessary, a polyol, and a catalyst were blended to prepare each main agent. Further, as shown in Tables 1 and 2 described later, each curing agent was prepared by blending a urethane prepolymer, and, if necessary, a polyisocyanate and a plasticizer. Then, the predetermined resin and the predetermined curing agent were sufficiently mixed at 25 ° C. to obtain a curable resin composition of each sample. In addition, since the curable resin composition of sample 2C used solid (meth) acrylic-type polyol (2) at 25 degreeC, it is necessary to mix, heating at the time of preparation of a curable resin composition, and an operation | work The sex was bad. Therefore, for the curable resin composition of sample 2C, the following experimental procedure was not performed.

  Next, each of the obtained curable resin compositions was poured into a No. 3 dumbbell-shaped mold of rubber and cured at 120 ° C. for 3 hours to obtain a cured product of each sample.

<Heat and humidity resistance>
A tensile test was performed on each cured product. The tensile test was performed under conditions of a tensile speed of 200 mm / min at 25 ° C. using “Autograph” manufactured by Shimadzu Corporation. Each cured product was also subjected to a pressure cooker (PCT) test. The conditions for the pressure cooker test were as follows: each cured product was placed in a test tank at 121 ° C., 2 atm, 100% humidity for 168 hours. A tensile test was carried out in the same manner as described above for each cured product subjected to the pressure cooker test. And storage-elastic-modulus E 'of the hardened | cured material before and behind a pressure cooker test was measured, and storage-elastic-modulus E' retention was calculated | required. The storage modulus E ′ retention was calculated from the formula 100 × (storage modulus E ′ of cured product after pressure cooker test) / (storage modulus E ′ of cured product before pressure cooker test). When the storage elastic modulus E ′ retention is 90% or more, “A +” is regarded as having excellent heat and humidity resistance, and the storage elastic modulus E ′ retention is 60% or more and less than 90%. The case where "A" had moisture heat resistance and the storage elastic modulus E 'retention rate was less than 60% was determined as "C" as having no moisture heat resistance.

Flexibility at low temperatures
By curing each of the curable resin compositions described above at 120 ° C. for 3 hours, strip-like cured products of 40 mm long × 5 mm wide × 1 mm thick were obtained. The viscoelasticity measurement was performed about each obtained hardened | cured material, and the temperature used as the inflexion point of an elastic modulus was made into glass transition temperature Tg. The conditions of the viscoelasticity measurement were a temperature increase rate of 5 ° C./min, a strain of 1%, and a frequency of 1 Hz between −100 ° C. and 25 ° C. Further, as the viscoelasticity measuring apparatus, “Leobybron DDV-25 FP” manufactured by Orientec Co., Ltd. was used. When the Tg is −50 ° C. or less, “A +” is excellent as the flexibility at low temperature, and when the Tg is more than −50 ° C. and −40 ° C or less as the flexibility at low temperature is good The case where "A" and Tg were more than -40 degreeC was determined as "C" as inferior to flexibility at low temperature. In addition, the hardened | cured material in which the determination of "A +" and "A" was made is considered to have sufficient flexibility at low temperature.

<Initial fracture strength>
A tensile test was carried out under the same conditions as above for each of the dumbbell-shaped cured products described above. And the intensity | strength at the time of a hardened | cured material fractured was made into the initial stage breaking strength of the hardened | cured material. When the initial breaking strength is 1 MPa or more, “A +” is excellent as the initial breaking strength, and “A” is good when the initial breaking strength is 0.2 MPa or more and less than 1 MPa as the initial breaking strength is good. When the initial breaking strength was less than 0.2 MPa, it was determined to be "C" as being inferior to the initial breaking strength.

  Tables 1 and 2 collectively show detailed blending of the curable resin composition, evaluation results of the cured product, and the like.

  According to Tables 1 and 2, the cured products of Samples 1 to 9 obtained by curing the curable resin composition having the configuration of Samples 1 to 9 have moist heat resistance, and are sufficiently flexible at low temperatures. It can be seen that it has good initial strength. Therefore, if this is used, for example, as a sealing material or an adhesive layer in an electrical component of a vehicle, it can be said that it is advantageous for improving the long-term insulation reliability of the electrical component.

  On the other hand, the curable resin composition of sample 1C does not contain a urethane prepolymer. Therefore, the curable resin composition of sample 1C was a cured product inferior in initial strength. In addition, as described above, the curable resin composition of Sample 2C had poor workability at the time of preparation of the composition.

  The present invention is not limited to the above embodiments and experimental examples, and various modifications can be made without departing from the scope of the invention. Moreover, each structure shown by each embodiment and each experiment example can each be combined arbitrarily.

1 Electrical component 11 Case 2 Sealant 3 Substrate

Claims (7)

(Meth) acrylic polyols,
And urethane prepolymer, and
The (meth) acrylic polyol is
A polymer having a hydroxyl value of 5 mgKOH / g or more and 150 mgKOH / g or less, a glass transition temperature of -70 ° C or more and -40 ° C or less, a number average molecular weight of 500 or more and 20000 or less, and liquid at 25 ° C;
The above urethane prepolymer is
A first structural unit derived from at least one polyol selected from the group consisting of a polycarbonate-based polyol, a castor oil-based polyol, and a hydrogenated polyolefin-based polyol, and a second structural unit derived from a polyisocyanate
Curable resin composition.   The curable resin composition according to claim 1, wherein the polyol is the polycarbonate-based polyol.   The curable resin composition according to claim 1, wherein a mass ratio of the (meth) acrylic polyol to the urethane prepolymer is 60:40 to 30:70.   The curable resin composition according to any one of claims 1 to 3, further comprising at least one polyol selected from the group consisting of polycarbonate polyols, castor oil polyols, and hydrogenated polyolefin polyols. .   Furthermore, the curable resin composition of any one of Claims 1-4 containing a polyisocyanate.   Electrical component (1) which has a sealing material (2) comprised from the hardened | cured material of the curable resin composition of any one of Claims 1-5. It has an adhesive layer that bonds the case and lid,
The said contact bonding layer is an electrical component comprised from the hardened | cured material of the curable resin composition of any one of Claims 1-5.

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