JP7087213B1 - Two-component curable polyurethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve tensile properties. A two-component curable polyurethane resin composition according to an embodiment contains a first component containing a polyol and a terpene resin, and a second component containing a polyisocyanate. The polyol contains 40% by mass or more of a polybutadiene polyol and / or a hydrogenated polybutadiene polyol, and further contains 4 to 15% by mass of an alkylene polyol having 7 or more and 9 or less carbon atoms. The content of the terpene resin is 5 to 60 parts by mass with respect to 100 parts by mass of the polyol. [Selection diagram] None

Description

The present invention relates to a two-component curable polyurethane resin composition, an electric / electronic component using the same, and a polyol composition for the two-component curable polyurethane resin composition.

Conventionally, electronic circuit boards and electronic components have been sealed with a polyurethane resin composition in order to protect them from external factors, and it is known that a polybutadiene polyol is used as the polyol of the polyurethane resin composition. ing.

For example, Patent Document 1 discloses an electrically insulating material composed of a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, a polycyclic aromatic hydrocarbon, and a petroleum resin. Patent Document 2 discloses a heat-resistant moisture-proof insulating coating material containing a polymer obtained by reacting a hydroxyl group-containing polybutadiene, a hydroxyl group-containing hydrogenated polybutadiene, and a polyisocyanate, a tackifier, and a solvent.

Patent Document 3 describes a two-component curable polyurethane resin composition containing a first component containing a polyol containing a polybutadiene polyol and a terpene resin, and a second component containing a polyisocyanate. Further, it is described that by using a terpene resin together with a polybutadiene polyol, compatibility is improved, adhesion to a substrate or the like is improved, and a polyurethane resin having a low dielectric constant can be obtained.

Japanese Unexamined Patent Publication No. 61-197620 Japanese Unexamined Patent Publication No. 8-165454 Japanese Patent No. 6916404

As described above, according to the invention described in Patent Document 3, a two-component curable polyurethane resin composition having excellent compatibility, adhesion and low dielectric properties is provided, but it cannot be said to be sufficient in terms of tensile properties. It has been found.

In view of the above points, it is an object of the present invention to provide a two-component curable polyurethane resin composition capable of improving tensile properties.

The present invention includes embodiments shown below.
[1] A first component containing a polyol and a terpene resin and a second component containing a polyisocyanate are contained, the polyol contains 40% by mass or more of a polybutadiene polyol and / or a hydrogenated polybutadiene polyol, and the polyol is. Further, a two-component curable polyurethane resin composition containing 4 to 15% by mass of an alkylene polyol having 7 or more and 9 or less carbon atoms and having a content of the terpene resin of 5 to 60 parts by mass with respect to 100 parts by mass of the polyol. thing.
[2] The two-component curable polyurethane resin composition according to [1], wherein the alkylene polyol is a diol having a hydroxy group bonded to a primary carbon atom and a hydroxy group bonded to a secondary carbon atom. ..
[3] The two-component curable polyurethane resin composition according to [1] or [2], wherein the polyisocyanate contains an aromatic polyisocyanate.
[4] The two-component curable polyurethane resin composition according to any one of [1] to [3], wherein the polyol further contains a castor oil-based polyol.
[5] The two-component curable polyurethane resin composition according to any one of [1] to [4], which is used for encapsulating electrical and electronic components.
[6] An electrical and electronic component resin-sealed using the two-component curable polyurethane resin composition according to any one of [1] to [5].
[7] A polyol composition used as a polyol component of a two-component curable polyurethane resin composition, which contains a polyol and a terpene resin, and the polyol contains 40% by mass or more of a polybutadiene polyol and / or a hydrogenated polybutadiene polyol. The polyol further contains 4 to 15% by mass of an alkylene polyol having 7 or more and 9 or less carbon atoms, and the content of the terpene resin is 5 to 60 parts by mass with respect to 100 parts by mass of the polyol. thing.

According to an embodiment of the present invention, it is possible to provide a two-component curable polyurethane resin composition capable of improving tensile properties.

The two-component curable polyurethane resin composition according to the present embodiment is a polyurethane resin composition containing a first component containing a polyol (A) and a terpene resin (B) and a second component containing a polyisocyanate (C). The polyol (A) contains a polybutadiene polyol (A1-1) and / or a hydrogenated polybutadiene polyol (A1-2) and an alkylene polyol (A2) having 7 or more and 9 or less carbon atoms.

<First component>
[Polybutadiene polyol (A1-1) and / or hydrogenated polybutadiene polyol (A1-2)]
The polyol (A) contained in the first component may be a polybutadiene polyol (A1-1) and / or a hydrogenated polybutadiene polyol (A1-2) (hereinafter, both are collectively referred to as "PB polyol (A1)". .) Is used.

The polybutadiene polyol (A1-1) preferably has a polybutadiene structure having a 1,4-bonded type, a 1,2-linked type or a mixture thereof and at least two hydroxy groups in the molecule, and both ends of the polybutadiene structure. It is more preferable that each of them has a hydroxy group.

The hydroxyl value of the polybutadiene polyol (A1-1) may be, for example, 10 to 200 mgKOH / g, 15 to 150 mgKOH / g, or 20 to 120 mgKOH / g. From the viewpoint of adhesion and compatibility, the hydroxyl value of the polybutadiene polyol (A1-1) is preferably 25 to 100 mgKOH / g, more preferably 40 to 90 mgKOH / g. In the present specification, the hydroxyl value is measured according to the method A of JIS K1557-1: 2007.

The hydrogenated polybutadiene polyol (A1-2) has a structure in which hydrogenation is added to the polybutadiene polyol (A1-1), and some or all of the unsaturated double bonds contained in the polybutadiene polyol are water. It is attached. The degree of hydrogenation of the hydrogenated polybutadiene polyol (A1-2) is not particularly limited, and for example, the iodine value may be 50 g / 100 g or less, or 30 g / 100 g or less. In the present specification, the iodine value is measured according to JIS K0070: 1992.

The hydroxyl value of the hydrogenated polybutadiene polyol (A1-2) may be, for example, 10 to 200 mgKOH / g, 15 to 150 mgKOH / g, 20 to 120 mgKOH / g, 25 to 100 mgKOH / g, or 40 to 90 mgKOH. It may be / g.

As the PB polyol (A1), it is more preferable to use a polybutadiene polyol (A1-1) from the viewpoint of tensile strength.

[Alkylene polyol (A2)]
As the polyol (A) contained in the first component, an alkylene polyol (A2) having 7 to 9 carbon atoms is used together with the PB polyol (A1). By adding the alkylene polyol (A2), the tensile properties, particularly the elongation rate can be improved.

The alkylene polyol (A2) having 7 to 9 carbon atoms may be a diol having two hydroxy groups in one molecule, or may have three or more hydroxy groups, but is preferably a diol. Specific examples of the alkylene polyol (A2) having 7 to 9 carbon atoms include 1,7-heptanediol, 1,2-heptanediol, 2,3-heptanediol, 5-methyl-2,4-hexanediol, and 2, -Methyl-2,5-hexanediol, 2,4-dimethyl-2,4-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2-ethyl-1,5-pentanediol, 2-ethyl Heptanediol such as -1,3-pentanediol; 1,8-octanediol, 1,2-octanediol, 1,3-octanediol, 1,4-octanediol, 2,4-octanediol, 2-methyl -1,2-Heptanediol, 2-Methyl-1,3-Heptanediol, 2-Methyl-2,3-Heptanediol, 2-Ethyl-1,2-hexanediol, 2-Ethyl-1,3-hexane Dire, 2-ethyl-1,5-hexanediol, 2-ethyl-1,6-hexanediol, 2,5-dimethyl-2,5-hexanediol, 3,4-dimethyl-3,4-hexanediol, Octanediol such as 2,5-dimethyl-3,4-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-propyl-1,2-pentanediol; 1,9-nonanediol, 1,2-Nonanediol, 2-methyl-1,8-octanediol, 2-ethyl-1,4-heptanediol, 2,6-dimethyl-3,5-heptanediol, 2,6-dimethyl-2, Examples thereof include nonanediol such as 6-heptanediol and 2-butyl-2-ethyl-1,3-propanediol. Any one of these may be used, or two or more thereof may be used in combination.

As the alkylene polyol (A2), it is preferable to use a diol having a hydroxy group bonded to a primary carbon atom and a hydroxy group bonded to a secondary carbon atom. Examples of such diols include 1,2-heptanediol, 2-ethyl-1,3-pentanediol, 1,2-octanediol, 1,3-octanediol, 1,4-octanediol, and 2-. Methyl-1,3-heptanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,5-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2- Examples include nonanediol and 2-ethyl-1,4-heptanediol. Any one of these may be used, or two or more thereof may be used in combination.

Among these, branched alkylene diols are preferable. The branched alkylene diol is an alkylene diol having a tertiary carbon atom and / or a quaternary carbon atom in the molecule. Specifically, 2-ethyl-1,3-pentanediol, 2-methyl-1,3-heptanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,5-hexanediol, 2 , 2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,4-heptanediol. More preferably, a diol having a tertiary carbon atom in the molecule and having a hydroxy group bonded to the primary carbon atom and a hydroxy group bonded to the secondary carbon atom is used.

[Castor oil-based polyol (A3)]
The polyol (A) may further contain a castor oil-based polyol (A3). By adding castor oil polyol (A3), the effect of improving tensile properties can be enhanced. As the castor oil-based polyol (A3), a polyol produced by using castor oil, castor oil fatty acid, hydrogenated castor oil or hydrogenated castor oil fatty acid can be used. More specifically, castor oil-based polyols (A3) include, for example, castor oil, transesterified castor oil and other natural fats and oils, reaction products of castor oil and polyhydric alcohols, and esterification of castor oil fatty acids and polyhydric alcohols. Examples thereof include reactants and polyols obtained by addition-polymerizing alkylene oxide to these.

The hydroxyl value of the castor oil-based polyol (A2) is not particularly limited, and may be, for example, 50 to 250 mgKOH / g or 100 to 180 mgKOH / g.

[Polyol (A)]
The polyol (A) may be composed only of PB polyol (A1) and alkylene polyol (A2), or may be composed only of PB polyol (A1), alkylene polyol (A2) and castor oil-based polyol (A3). In addition to these, other polyols (A4) may be contained. The polyol (A) may be composed of only bifunctional ones or may contain trifunctional or higher functional ones, but when the polyisocyanate (C) is composed of only bifunctional ones, the polyurethane resin composition It is preferable to contain a trifunctional or higher functional polyol so as to be thermosetting.

Examples of the other polyol (A4) are compounds having a plurality of hydroxy groups in the molecule, and examples thereof include various polyols other than PB polyol (A1), alkylene polyol (A2) and castor oil-based polyol (A3). Specific examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, dimer acid polyols, polycaprolactone polyols, acrylic polyols, polyisoprene polyols, hydrogenated polyisoprene polyols and the like. Also, low molecular weight polyols commonly used as cross-linking agents, such as N, N-bis (2-hydroxypropyl) aniline, hydroquinone-bis (β-hydroxyethyl) ethers, resorcinol-bis (β-hydroxyethyl) ethers. Aromatic alcohols such as.

The content of the PB polyol (A1) in 100% by mass of the polyol (A) is 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more. When the content of the PB polyol (A1) is 40% by mass or more, the adhesion to the electronic circuit board or the like can be improved, and the dielectric constant can be lowered. The content of the PB polyol (A1) is 96% by mass or less, preferably 92% by mass or less, 90% by mass or less, 85% by mass or less, or 80% by mass or less.

The content of the alkylene polyol (A2) in 100% by mass of the polyol (A) is 4 to 15% by mass. When the content of the alkylene polyol (A2) is 4% by mass or more, the tensile properties can be improved, and when it is 15% by mass or less, deterioration of compatibility can be suppressed. The content of the alkylene polyol (A2) is preferably 5% by mass or more, preferably 12% by mass or less, and more preferably 10% by mass or less.

When the castor oil-based polyol (A3) is contained in the polyol (A), the content of the castor oil-based polyol (A3) in 100% by mass of the polyol (A) may be, for example, 4 to 56% by mass, or 10 to 40% by mass. It may be%, and it may be 15 to 30% by mass.

[Terpene resin (B)]
The first component contains a terpene resin (B) together with a PB polyol (A1) and an alkylene polyol (A2). Since the terpene resin (B) has excellent compatibility with the PB polyol (A1), it is possible to suppress the separation and turbidity of the first component. Further, by blending the terpene resin (B) together with the PB polyol (A1) and the alkylene polyol (A2), the adhesion to the electronic circuit substrate or the like can be improved, and the low dielectric property and the tensile property (particularly). This will lead to an improvement in the growth rate).

The terpene resin (B) is a polymer containing terpene as a constituent monomer. Examples of terpenes (also referred to as terpene monomers) include α-pinene, β-pinene, limonene (including racemic dipentene), milsen, aloosimene, osimene, α-pherandrene, β-pherandrene, and α-. Examples thereof include monoterpenes such as terpinene, γ-terpinene, and sabinen, and any one or two or more of these can be used in combination. Among these, monoterpene monoterpenes such as α-pinene, β-pinene, limonene, α-phellandrene, β-pherandrene, α-terpinene, and γ-terpinene are preferable, and α-pinene is more preferable. At least one selected from the group consisting of β-pinene and limonene.

The terpene resin (B) includes a polyterpene resin (B1) which is a homopolymer or a copolymer composed of only a terpene monomer as a constituent monomer, and an aromatic-modified terpene resin (B1) which is a copolymer of a terpene monomer and an aromatic monomer. B2), a terpene phenol resin (B3) which is a copolymer of a terpene monomer and a phenolic monomer can be mentioned. Any one of these may be used, or two or more thereof may be used in combination.

Examples of the aromatic monomer constituting the aromatic-modified terpene resin (B2) include styrene, α-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene and the like as the aromatic monomer.

Examples of the phenolic monomer constituting the terpene phenol resin (B3) include phenol, cresol, xylenol and the like.

Preferable examples of the terpene resin (B) are polyterpene resin (B1) and α-pinene, which are at least one homopolymer or copolymer selected from the group consisting of α-pinene, β-pinene and limonene. , Β-Pinene and limonene from the group consisting of aromatic-modified terpene resin (B2), α-pinene, β-pinene and limonene, which is a copolymer of at least one terpene monomer selected from the group consisting of styrene. Included is a terpene phenolic resin (B3), which is a copolymer of at least one selected terpene monomer and phenol.

The content of the terpene resin (B) is 5 to 60 parts by mass with respect to 100 parts by mass of the polyol (A). When the content of the terpene resin (B) is 60 parts by mass or less, the bleeding of the terpene resin (B) after the polyurethane resin is cured can be suppressed. The content of the terpene resin (B) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more. The content of the terpene resin (B) is preferably 50 parts by mass or less, and may be 45 parts by mass or less.

[Other ingredients]
In addition to the above-mentioned components, the first component may include, for example, a catalyst, an antioxidant, a foam stabilizer, a diluent, a flame retardant, an ultraviolet absorber, a colorant, a filler, a plasticizer, etc. Various additives can be added as long as the object of the present embodiment is not impaired.

As the catalyst, for example, an organic tin catalyst, an organic lead catalyst, a metal catalyst such as an organic bismuth catalyst, and various urethane polymerization catalysts such as an amine catalyst can be used.

<Second component>
[Polyisocyanate (C)]
The polyisocyanate (C) contained in the second component is not particularly limited, and various polyisocyanate compounds having two or more isocyanate groups in one molecule can be used. Examples of the polyisocyanate (C) include aromatic polyisocyanate (C1), aliphatic polyisocyanate (C2), and alicyclic polyisocyanate (C3), and even if any one of these is used, 2 You may use more than seeds together.

Examples of the aromatic polyisocyanate (C1) include toluene diisocyanate (TDI, for example 2,4-TDI, 2,6-TDI) and diphenylmethane diisocyanate (MDI, for example 2,2'-MDI, 2,4'-. MDI, 4,4'-MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate (XDI), 1,3-phenylenedi isocyanate, 1,4-phenylenedi isocyanate, and these. Denatured and polynuclear bodies of.

Examples of the aliphatic polyisocyanate (C2) include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine. Examples thereof include diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, and modified and polynuclear bodies thereof.

Examples of the alicyclic polyisocyanate (C3) include isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexanediisocyanate, methylcyclohexylene diisocyanate, and 1,3-. Includes bis (isocyanate methyl) cyclohexane, as well as modified and polynuclear compounds thereof.

Examples of the modified product include isocyanurate modified product, allophanate modified product, burette modified product, adduct modified product, carbodiimide modified product and the like.

In one embodiment, the polyisocyanate (C) preferably contains an aromatic polyisocyanate (C1). By using the aromatic polyisocyanate (C1), the effect of improving the tensile properties can be enhanced. More preferably, as the polyisocyanate (C), at least one selected from the group consisting of diphenylmethane diisocyanate and its modified and polynuclear bodies is used.

The content of the polyisocyanate (C) in the two-component curable polyurethane resin composition is not particularly limited, and may be, for example, 1 to 70 parts by mass with respect to 100 parts by mass of the polyol (A), and 3 to 50 parts by mass. It may be 5 to 40 parts by mass.

The polyisocyanate (C) may be composed of only bifunctional ones or may contain trifunctional or higher functional ones, but when the polyol (A) is composed of only bifunctional ones, the polyurethane resin composition It is preferable to contain a trifunctional or higher polyisocyanate so as to be thermosetting.

The ratio of the polyisocyanate (C) to the polyol (A) is not particularly limited, and for example, the NCO / OH (index) may be 0.6 to 1.5 or 0.7 to 1.4. It may be 0.8 to 1.3 or 0.9 to 1.2. Here, NCO / OH is the molar ratio of the isocyanate group contained in the polyisocyanate (C) to the hydroxy group contained in the polyol (A). NCO / OH is calculated using the hydroxyl value of the polyol (A) and the isocyanate value of the polyisocyanate (C). The isocyanate value is calculated by isocyanate value = {(isocyanate content) × 56110} / (42.02 × 100) using the isocyanate content measured according to the method A of JIS K1603-1: 2007. To.

[Other ingredients]
The second component may be composed of only the polyisocyanate (C), and in addition to the polyisocyanate (C), for example, a catalyst, an antioxidant, a foam stabilizer, a diluent, and a flame retardant. , UV absorbers, colorants, fillers, plasticizers and the like may be added as long as the object of the present embodiment is not impaired.

<Two-component curable polyurethane resin composition>
The two-component curable polyurethane resin composition according to the present embodiment is usually composed of a first liquid as a first component and a second liquid as a second component, but the first component and the second component In addition, a third component containing the above-mentioned other components as an optional component may be provided as the third liquid.

The two-component curable polyurethane resin composition can be produced by preparing the first component and the second component, respectively, that is, even if the first component and the second component are filled in different containers. good. The first component and the second component filled in separate containers may be mixed at the time of use to react the polyol (A) and the polyisocyanate (C) to form a polyurethane resin, which may be cured. At that time, it may be cured by heating. The two-component curable polyurethane resin composition according to the embodiment may be obtained by mixing the first component and the second component, may be a liquid before curing, or may be cured.

<Polyol composition>
The polyol composition according to one embodiment is used as a polyol component of a two-component curable polyurethane resin composition, and the first component corresponds to this. Therefore, the polyol composition contains a polyol (A) and a terpene resin (B), and the polyol (A) contains 40% by mass or more of a polybutadiene polyol and / or a hydrogenated polybutadiene polyol (A1), and the polyol (A). ) Further contains 4 to 15% by mass of the alkylene polyol (A2) having 7 to 9 carbon atoms, and the content of the terpene resin (B) is 5 to 60 parts by mass with respect to 100 parts by mass of the polyol (A). Details of the polyol (A), the terpene resin (B) and other components are as described above, and the description thereof will be omitted.

<Use of two-component curable polyurethane resin composition>
The use of the two-component curable polyurethane resin composition according to the present embodiment is not particularly limited, but it is preferably used for sealing electric and electronic parts. Examples of electrical and electronic components include transformers such as transformer coils, choke coils and reactor coils, device control boards, sensors, wireless communication components and the like. The two-component curable polyurethane resin composition has excellent low dielectric properties (that is, has a low dielectric constant) and is not easily affected by radio waves. Therefore, it is preferable that the two-component curable polyurethane resin composition is used as a sealing material for resin-sealing, that is, covering the wireless communication component in order to protect the wireless communication component that performs wireless communication from the external environment. For example, it may be used as a sealing material for a sensor that transmits the detected information by wireless communication.

The electric and electronic parts resin-sealed using the two-component curable polyurethane resin composition according to the present embodiment include, for example, an electric washing machine, a toilet seat, a water heater, a water purifier, a bath, a dishwasher, a solar panel, and the like. It can be used for electric tools, automobiles, motorcycles, etc.

Hereinafter, the two-component curable polyurethane resin composition will be described in detail based on Examples and Comparative Examples, but the present invention is not limited thereto.

The raw materials used in Examples and Comparative Examples are shown below.

[Polyol (A)]
-Polybutadiene polyol 1: hydroxyl value 47 mgKOH / g, product name: Poly bd R-45HT, manufactured by Idemitsu Kosan Co., Ltd.-Polybutadiene polyol 2: hydroxyl value 107 mgKOH / g, product name: Poly bd R-15HT, Idemitsu Kosan Co., Ltd. ) Manufactured by hydrogenated polybutadiene polyol: hydroxyl value 49 mgKOH / g, product name: KRASOL H-LBH-2000, manufactured by Clay Valley Co., Ltd. Octanediol: 2-ethyl-1,3-hexanediol, product name: octanediol, KH Neochem Co., Ltd., Trimethylol Propane: Tokyo Kasei Kogyo Co., Ltd., Product code T0480
・ 1,10-Decandiol: Made by Tokyo Chemical Industry Co., Ltd., Product code D0014
-Ethylene glycol: manufactured by Nacalai Tesque Co., Ltd., product code 15208-95
1,4-Butanediol: manufactured by Nacalai Tesque Co., Ltd., product code 0592-35
-Castor oil-based polyol: Hydroxy group value 160 mgKOH / g, Product name: Castor oil, manufactured by Itoh Oil Chemicals Co., Ltd.

[Terpene resin (B)]
-Terpene resin 1: Limonen-styrene copolymer, active ingredient 50% by mass, product name: YS resin LP, manufactured by Yasuhara Chemical Co., Ltd.-Terpene resin 2: pinen-dipentene copolymer, active ingredient 80% by mass, product name : Daimaron, manufactured by Yasuhara Chemical Co., Ltd. ・ Terpene resin 3: Phenol / α-pinene copolymer, 100% by mass of active ingredient, product name: YS POLYSTER T80, manufactured by Yasuhara Chemical Co., Ltd.

[Polyisocyanate (C)]
-Aromatic polyisocyanate: Polymeric MDI, Product name: Millionate MR-200, manufactured by Tosoh Corporation

[Examples 1 to 12 and Comparative Examples 1 to 7]
The two-component curable polyurethane resin compositions of each Example and each Comparative Example were prepared according to the formulations (parts by mass) shown in Tables 1 and 2 below. At the time of preparation, the first component shown in Tables 1 and 2 was weighed in a predetermined amount, and the mixture was stirred and mixed while being melted by appropriately applying heat, and after mixing, the temperature was adjusted to 25 ° C. Subsequently, a second component (polyisocyanate (C)) adjusted to 25 ° C. was added to this mixture as shown in Tables 1 and 2, and the mixture was stirred and mixed to defoam.

For each two-component curable polyurethane resin composition, compatibility, adhesion, dielectric constant, tensile strength, and elongation were measured and evaluated. The measurement / evaluation method is as follows.

[Compatibility]
Using the liquid after mixing the first component, use two screw tube bottles (No. 7 manufactured by Maruemu Co., Ltd.) with a diameter of 3 cm, one with a height of 10 cm and the other with a height of 1 cm. I poured it to be. Each screw tube bottle was placed on a paper on which the letter "S" (MS Gothic, 12 points) was printed, and the compatibility was evaluated in the following three stages A to C by visually recognizing the letter from above. If the first component is separated after preparation, the compatibility between the polyol and the resin is poor, and subsequent measurement and evaluation as a two-component curable polyurethane resin composition cannot be carried out. The evaluation result was described as D, and no further evaluation was carried out. If the evaluation is C or higher, it can be said that the product has practical compatibility.
A: Transparent (10 cm in height, 1 cm in height, any screw tube bottle can read the letters written below)
B: Slightly turbid (I cannot read the letters written under the screw tube bottle with a height of 10 cm, but I can read the letters written under the screw tube bottle with a height of 1 cm)
C: White turbidity (the letters written below cannot be read with any screw tube bottle with a height of 10 cm or 1 cm)

[Adhesion]
The two-component curable polyurethane resin composition after defoaming was dropped on a commercially available FR-4 epoxy substrate with a diameter of about 1 cm, and cured at 80 ° C. for 16 hours (overnight) to be cured. Aiming at the boundary between the cured polyurethane resin and the epoxy substrate, the resin was scraped with a cutter knife, and the polyurethane resin remaining on the substrate was visually confirmed. In the evaluation, the cohesive failure is the state where the polyurethane resin part remains on the substrate, and the interface peeling is the state where the polyurethane resin is peeled off from the substrate. When both states are mixed, the following is performed according to the area ratio. Evaluation was performed according to the criteria. If the evaluation is D or higher, it can be said that the product has practical adhesion.
A: 100% coagulation failure
B: Aggregate fracture is 75% or more and less than 100%, interfacial peeling is more than 0% and 25% or less C: Aggregate fracture is 50% or more and less than 75%, interfacial peeling is more than 25% and 50% or less D: Aggregate fracture is 25% or more Less than 50%, interfacial peeling is more than 50% and 75% or less E: Aggregate fracture is less than 25%, interfacial peeling is 75% or more

[Dielectric constant]
The two-component curable polyurethane resin composition after defoaming was poured into a mold having a thickness of 3 mm and cured at 80 ° C. for 16 hours (overnight) to prepare a resin sheet having a thickness of 3 mm. The resin sheet was cut into 50 mm × 50 mm × 3 mm sheets and used as a measurement sample. The measurement was carried out using a device manufactured by Agilent Technologies Co., Ltd. (main body model: E4980A, name: Precision LCR Meter, electrode part model: 16451B, name: DIELECTRIC TEST FIXTURE), and the dielectric constant at a frequency of 1 MHz. The value of (relative permittivity) was measured and evaluated according to the following criteria.
A: Permittivity is 2.8 or less B: Permittivity is greater than 2.8 and 3.0 or less C: Permittivity is greater than 3.0 and 3.2 or less D: Permittivity is greater than 3.2 and 3.4 Below E: Permittivity is greater than 3.4

[Tensile strength, elongation]
The two-component curable polyurethane resin composition after defoaming was poured into a mold having a thickness of 3 mm and cured at 80 ° C. for 16 hours (overnight) to prepare a resin sheet having a thickness of 3 mm. The resin sheet was punched into a dumbbell-shaped No. 3 mold to prepare a sample for measurement. For measurement, use a device manufactured by Shimadzu Corporation (main unit model: AG-X Plus, name: Shimadzu Precision Universal Testing Machine Autograph), set the tensile speed to 500 mm / min, and set the chuck distance to 40 mm. It was carried out three times, and the average values of tensile strength (breaking stress) and elongation (breaking elongation) were calculated and evaluated according to the following criteria.
(Evaluation criteria for tensile strength)
A: Tensile strength is 3.0 MPa or more B: Tensile strength is 2.5 MPa or more and less than 3.0 MPa C: Tensile strength is 2.0 MPa or more and less than 2.5 MPa D: Tensile strength is 1.5 MPa or more and less than 2.0 MPa Less than E: Tensile strength is less than 1.5 MPa (evaluation standard for elongation)
A: Elongation rate is 130% or more B: Elongation rate is 110% or more and less than 130% C: Elongation rate is 90% or more and less than 110% D: Elongation rate is 70% or more and less than 90% E: Elongation rate is 70 %Less than

The results are shown in Tables 1 and 2. In Comparative Example 1, by using the PB polyol (A1) and the terpene resin (B) in combination, the compatibility was excellent, the low dielectric property and the adhesion to the substrate were also excellent, but the alkylene polyol (A2) was blended. The tensile strength and elongation were low, and the tensile properties were inferior.

On the other hand, in Examples 1 to 12 to which the alkylene polyol (A2) was added, compatibility, adhesion and low dielectric properties were obtained, and tensile properties could be further improved. In particular, Examples 1 and 4 to 12 are excellent in compatibility, adhesion and low dielectric properties, and are also excellent in the effect of improving tensile properties. Further, Examples 1, 5 and 7 to 11 are more excellent. An even better effect was seen. In Example 3, the evaluation of the tensile strength was D, but the evaluation of the elongation rate was excellent at A, and the effect of improving the tensile properties was recognized as a whole.

In Comparative Examples 2 to 5, other alkylene polyols such as trimethylolpropane, decanediol, ethylene glycol or butanediol were added in place of the alkylene polyol (A2) having 7 to 9 carbon atoms. In these comparative examples, the effect of improving the tensile properties was not obtained even in Comparative Example 3 in which the compatibility was impaired or the compatibility was good.

It should be noted that the various numerical ranges described in the specification can be arbitrarily combined with the upper limit value and the lower limit value, respectively, and it is assumed that all combinations thereof are described in the present specification as a preferable numerical range. Further, the description of the numerical range of "X to Y" means X or more and Y or less.

Although some embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other embodiments, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments, omissions, replacements, changes, etc. thereof are included in the scope and gist of the invention, as well as in the scope of the invention described in the claims and the equivalent scope thereof.

Claims (6)

The first component, including polyols and terpene resins,
Contains a second component, including polyisocyanate,
The polyol contains 40% by mass or more of a polybutadiene polyol and / or a hydrogenated polybutadiene polyol.
The polyol further includes 2-ethyl-1,3-pentanediol, 2-methyl-1,3-heptandiol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,5-hexanediol, 2 , 2,4-trimethyl-1,3-pentanediol, and 2 to 15% by weight of at least one alkylene polyol selected from the group consisting of 2-ethyl-1,4-heptandiol .
A two-component curable polyurethane resin composition in which the content of the terpene resin is 5 to 60 parts by mass with respect to 100 parts by mass of the polyol. The two-component curable polyurethane resin composition according to claim 1 , wherein the polyisocyanate contains an aromatic polyisocyanate. The two-component curable polyurethane resin composition according to claim 1 or 2 , wherein the polyol further contains a castor oil-based polyol. The two-component curable polyurethane resin composition according to any one of claims 1 to 3 , which is used for encapsulating electrical and electronic components. An electrical and electronic component resin-sealed using the two-component curable polyurethane resin composition according to any one of claims 1 to 4 . A polyol composition used as a polyol component of a two-component curable polyurethane resin composition.
Contains polyols and terpene resins
The polyol contains 40% by mass or more of a polybutadiene polyol and / or a hydrogenated polybutadiene polyol.
The polyol further includes 2-ethyl-1,3-pentanediol, 2-methyl-1,3-heptandiol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,5-hexanediol, 2 , 2,4-trimethyl-1,3-pentanediol, and 2 to 15% by weight of at least one alkylene polyol selected from the group consisting of 2-ethyl-1,4-heptandiol .
A polyol composition in which the content of the terpene resin is 5 to 60 parts by mass with respect to 100 parts by mass of the polyol.