CN111699217B - Polyurethane resin composition - Google Patents

Polyurethane resin composition Download PDF

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CN111699217B
CN111699217B CN201980011509.7A CN201980011509A CN111699217B CN 111699217 B CN111699217 B CN 111699217B CN 201980011509 A CN201980011509 A CN 201980011509A CN 111699217 B CN111699217 B CN 111699217B
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resin composition
polyurethane resin
polyol
mass
compound
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CN111699217A (en
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农宗辰己
森崎晃
叶狩奈津美
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Sanyu Rec Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes

Abstract

The invention aims to provide a polyurethane resin which is excellent in compatibility, workability and cold-heat cycle characteristics by using a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less. The present invention relates to a polyurethane resin composition containing (A) a polyisocyanate compound, (B) a polyol compound, (C) an inorganic filler, and (D) a plasticizer, wherein the polyol compound (B) contains (B1) a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less, and contains 50 to 85 mass% of the inorganic filler (C) and 1 to 30 mass% of the plasticizer (D) per 100 mass% of the polyurethane resin composition.

Description

Polyurethane resin composition
Technical Field
The present invention relates to a polyurethane resin composition.
Background
In recent years, with the progress of electronic circuit boards and electronic components, stress applied to the components by heat and cold cycles has increased, and there is a need for components that can maintain high heat resistance and long-term heat dissipation.
Polyurethane resins used for sealing these members have a problem that they lose flexibility and crack due to long-term cooling and heating cycles, and there is an urgent need to develop a member which can maintain its elastic modulus for a long period of time while further reducing its temperature dependence.
For example, patent documents 1 to 3 describe the use of a polybutadiene polyol having a hydroxyl value of 20 to 120 mgKOH/g. However, these documents do not specifically disclose a polyurethane resin using a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less, and it is preferable to use a polybutadiene polyol having a hydroxyl value of 100mgKOH/g or more (Poly bd (registered trademark) R-15HT, etc.) as the polyol compound.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-020439
Patent document 2: japanese laid-open patent publication No. 2015-131883
Patent document 3: japanese laid-open patent publication (Kokai) No. 2015-089944
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a polyurethane resin that has appropriate hardness, excellent compatibility, workability, elongation, elastic modulus (-40 ℃ elastic modulus (10Hz)), and volume resistance, and excellent cold-heat cycle characteristics (-40 ℃ to 120 ℃ elastic modulus change), using a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less.
Means for solving the problems
The present inventors have made extensive studies to solve the above problems, and as a result, they have found that the above problems can be solved by using a polyurethane resin composition containing a polyol compound comprising a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less and containing 50 to 85 mass% of an inorganic filler and 1 to 30 mass% of a plasticizer with respect to 100 mass% of the polyurethane resin composition. The present invention has been completed based on the above findings.
That is, the present invention relates to the following polyurethane resin composition, sealing material, electric and electronic parts, and the like.
Item 1.
A polyurethane resin composition comprising (A) a polyisocyanate compound, (B) a polyol compound, (C) an inorganic filler and (D) a plasticizer,
the polyol compound (B) comprises (B1) a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less,
the polyurethane resin composition contains (C) 50-85 mass% of an inorganic filler and (D) 1-30 mass% of a plasticizer, based on 100 mass% of the polyurethane resin composition.
Item 2.
The polyurethane resin composition according to item 1, wherein the change in elastic modulus ([ -elastic modulus at 40 ℃ - [ elastic modulus at 120 ℃) is 40MPa or less.
Item 3.
The polyurethane resin composition according to item 1 or 2, wherein the change in elastic modulus ([ -elastic modulus at 40 ℃ - [ elastic modulus at 120 ℃) is 30MPa or less.
Item 4.
The polyurethane resin composition according to any one of items 1 to 3, wherein the polyisocyanate compound (A) is an isocyanurate body of an aliphatic polyisocyanate compound, an alicyclic polyisocyanate, and/or an aromatic polyisocyanate.
Item 5.
The polyurethane resin composition according to any one of items 1 to 4, wherein the polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less (b1) is 5 to 15% by mass based on 100% by mass of the polyurethane resin composition.
Item 6.
The polyurethane resin composition according to any one of items 1 to 5, wherein the (B) polyol compound does not contain castor oil or castor oil-based polyol.
Item 7.
The polyurethane resin composition according to any one of items 1 to 6, wherein the (D) plasticizer does not contain an ester compound represented by general formula (1):
Figure BDA0002615244380000031
in the formula (1), R1And R2Each independently represents an alkyl group having 6 to 12 carbon atoms, and X represents an alkylene group having 3 to 8 carbon atoms. And a and b each independently represent an integer of 2 to 10, and the total of a and b is 4 to 20.
Item 8.
The polyurethane resin composition as recited in any one of items 1 to 7, wherein the polybutadiene polyol (b1) has a number average molecular weight (Mn) within a range of 100 to 5000.
Item 9.
The polyurethane resin composition according to any one of items 1 to 8, wherein the viscosity (30 ℃) of the polybutadiene polyol (b1) is in a range of 0.01 to 100Pa · s.
Item 10.
The polyurethane resin composition as claimed in any one of items 1 to 9, wherein the volume resistivity is 1 x 1012Omega cm or more.
Item 11.
The polyurethane resin composition according to any one of items 1 to 10, wherein an elastic modulus (10Hz) at-40 ℃ is 40MPa or less.
Item 12.
The polyurethane resin composition according to any one of items 1 to 11, wherein the polyurethane resin composition further contains (E) a crosslinking agent.
Item 13.
The polyurethane resin composition as claimed in any one of items 1 to 11, wherein the polyurethane resin composition further contains (E) a crosslinking agent (excluding castor oil).
Item 14.
The polyurethane resin composition according to item 12 or 13, wherein the (E) crosslinking agent is (E1) an aromatic alcohol-based crosslinking agent and/or (E2) an aliphatic alcohol-based crosslinking agent.
Item 15.
The polyurethane resin composition according to any one of claims 12 to 14, wherein the (E) crosslinking agent is (E1) an aromatic alcohol crosslinking agent.
Item 16.
The polyurethane resin composition according to any one of claims 12 to 15, wherein the crosslinking agent (E) is a crosslinking agent having a number average molecular weight of 400 or less.
Item 17.
The polyurethane resin composition according to any one of items 1 to 16, wherein the (D) plasticizer comprises (D1) an adipic acid-based plasticizer and/or (D2) a phthalic acid-based plasticizer.
Item 18.
The polyurethane resin composition according to any one of items 1 to 17, wherein the plasticizer (D) is an adipic acid-based plasticizer (D1).
Item 19.
The polyurethane resin composition according to any one of items 1 to 18, wherein the plasticizer (D) is contained in an amount of 10 to 29% by mass based on 100% by mass of the polyurethane resin composition.
Item 20.
A polyurethane resin composition comprising (A) a polyisocyanate compound, (B) a polyol compound, (C) an inorganic filler and (D) a plasticizer,
the polyisocyanate compound (A) is an isocyanurate of an aliphatic polyisocyanate compound, an alicyclic polyisocyanate, and/or an aromatic polyisocyanate,
the polyol compound (B) comprises (B1) a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less, and
the polyol compound (B) does not contain a castor oil or castor oil-based polyol,
the (D) plasticizer does not contain an ester compound represented by the general formula (1):
Figure BDA0002615244380000051
in the formula (1), R1And R2Each independently representAn alkyl group having 6 to 12 carbon atoms, and X represents an alkylene group having 3 to 8 carbon atoms. In addition, a and b each independently represent an integer of 2 to 10, the sum of a and b is 4 to 20,
the polyurethane resin composition comprises (b1) 5-15% by mass of a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less, (C) 50-85% by mass of an inorganic filler, and (D) 1-30% by mass of a plasticizer, based on 100% by mass of the polyurethane resin composition,
the change in elastic modulus ([ -elastic modulus at 40 ℃ C. ] - [ elastic modulus at 120 ℃ C. ]) is 30MPa or less.
Item 21.
The polyurethane resin composition according to any one of items 1 to 20, wherein the polyurethane resin composition is used for sealing an electric and electronic component.
Item 22.
A sealing material comprising the polyurethane resin composition as set forth in any one of claims 1 to 21.
Item 23.
An electric/electronic component resin-sealed with the sealing material according to item 22.
Effects of the invention
According to the present invention, a polyurethane resin composition and a sealing material can be provided which have appropriate hardness, excellent compatibility, workability, elongation, elastic modulus (-40 ℃ elastic modulus (10Hz)) and volume resistance, and excellent cold-heat cycle characteristics (-40 ℃ to 120 ℃ elastic modulus change).
Specifically, the polyurethane resin composition and the sealing material of the present invention can reduce the temperature dependence of the elastic modulus (120 ℃ C. to-40 ℃ C.) as the cold-heat cycle characteristics, exhibit excellent elongation (flexibility), and can suppress the change in hardness, elongation (flexibility), and elastic modulus (100 ℃ C.) due to thermal deterioration (after heat resistance).
Therefore, the polyurethane resin composition and the sealing material of the present invention can be suitably used for, for example, insulation treatment of various electric and electronic components.
Further, the electric/electronic component of the present invention exhibits high reliability because it is resin-sealed with the sealing material.
Detailed Description
The polyurethane resin composition, the sealing material and the electric/electronic component of the present invention will be described in detail below. In the present specification, the expression "including" or "including" includes the concepts of "including", "consisting essentially of" and "consisting of only.
1. Polyurethane resin composition
The polyurethane resin composition of the present invention comprises (A) a polyisocyanate compound, (B) a polyol compound, (C) an inorganic filler and (D) a plasticizer,
the polyol compound (B) comprises (B1) a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less,
the polyurethane resin composition contains (C) 50-85 mass% of an inorganic filler and (D) 1-30 mass% of a plasticizer, based on 100 mass% of the polyurethane resin composition.
The change in elastic modulus ([ -elastic modulus at 40 ℃ C. ] - [ elastic modulus at 120 ℃ C. ]) ] of the polyurethane resin composition of the present invention is preferably 40MPa or less, more preferably 30MPa or less, and particularly preferably 20MPa or less.
The volume resistivity of the polyurethane resin composition of the present invention is preferably 1X 1012Omega cm or more, more preferably 1X 1012Omega cm or more.
The polyurethane resin composition of the present invention has an elastic modulus at-40 ℃ (10Hz) of preferably 40MPa or less, more preferably 30MPa or less, and particularly preferably 20MPa or less.
1-1.(A) polyisocyanate compound
The "(a) polyisocyanate compound" is not particularly limited as long as it has 2 or more isocyanate groups, and various components used or usable in the urethane resin composition (particularly, the urethane resin composition for sealing electric and electronic components) can be used.
The polyisocyanate compound (a) is not particularly limited, and examples thereof include:
(A1) an aliphatic polyisocyanate compound,
(A2) An alicyclic polyisocyanate compound,
(A3) Aromatic polyisocyanate compound
Polyisocyanate compounds such as polyisocyanate compounds;
the modified body (a) of the above polyisocyanate compound (e.g.,
(a-1) isocyanurate compound,
(a-2) a carbodiimide compound,
(a-3) adduct,
(a-4) biuret compound,
(a-5) allophanate compounds, etc.);
and (b) a polynuclear body of the polyisocyanate compound.
Examples of the (a1) aliphatic polyisocyanate compound include: tetramethylene diisocyanate, dodecamethylene diisocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), 2, 4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1, 5-diisocyanate, 3-methylpentane-1, 5-diisocyanate, etc., preferably 1, 6-Hexamethylene Diisocyanate (HDI).
The aliphatic polyisocyanate compound (A1) is preferably an isocyanurate of an aliphatic polyisocyanate compound (A1 a-1). For example, as the isocyanurate-modified 1, 6-hexamethylene diisocyanate used in the present invention, an isocyanurate compound having an isocyanate group at the end derived from 1, 6-hexamethylene diisocyanate (hereinafter referred to as "HDI") is used. Specific examples of these include: DURANATE (registered trademark) TPA-100, DURANATE TKA-100, DURANATE TSA-100, DURANATE TSS-100, DURANATE TSE-100, DURANATE TLA-100, manufactured by Asahi Kasei corporation; DESMODUR (registered trademark) N3390 manufactured by sumitomo bayer urethane corporation; CORONATE (registered trademark) EH manufactured by japan polyurethane corporation; TAKENATE D170N manufactured by martian chemicals industries co; and BURNOCK (registered trademark) DN980 manufactured by Dainippon ink chemical industries, Ltd. (DIC Co., Ltd.).
Examples of the (a2) alicyclic polyisocyanate compound include: isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4 '-dicyclohexylmethane diisocyanate (hydrogenated product of 4, 4' -diphenylmethane diisocyanate, HMDI), 1, 4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, and the like.
As the hydrogenated product of 4,4 '-diphenylmethane diisocyanate used in the present invention, polyisocyanate obtained by hydrogenating 4, 4' -diphenylmethane diisocyanate (hereinafter abbreviated as MDI) is used. Specific examples of these include WANNATE (registered trademark) HMDI manufactured by Wawawa chemical Japan.
Examples of the (a3) aromatic polyisocyanate compound include: toluene diisocyanate, 2 ' -diphenylmethane diisocyanate, 2,4 ' -diphenylmethane diisocyanate, 4 ' -diphenylmethane diisocyanate (MDI), 4 ' -dibenzyl diisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, α, α -tetramethylxylylene diisocyanate, and the like, with 2 ' -diphenylmethane diisocyanate, 2,4 ' -diphenylmethane diisocyanate, and 4,4 ' -diphenylmethane diisocyanate (MDI) being preferred.
As the 4,4 '-diphenylmethane diisocyanate (MDI) used in the present invention, a polyisocyanate having a carbodiimide group derived from 4, 4' -diphenylmethane diisocyanate (carbodiimide-modified MDI) is used. Specific examples of these include MILLIONATE (registered trademark) MTL manufactured by Tosoh corporation.
(A) The viscosity of the polyisocyanate compound is not particularly limited, and may vary greatly depending on the type of the polyisocyanate compound, whether it is modified, and the like. For example, in the case of the aromatic polyisocyanate compound and the modified product thereof and the polynuclear compound (preferably, the carbodiimide compound and the polynuclear compound of the aromatic polyisocyanate compound), the viscosity at 25 ℃ is, for example, 5 to 200 mPas, preferably 10 to 150 mPas, more preferably 15 to 100 mPas, and further preferably 20 to 80 mPas. As another example, in the case of the aliphatic polyisocyanate compound, a modified product thereof, and a polynuclear body (preferably, an isocyanurate body of the aliphatic polyisocyanate compound), the viscosity at 25 ℃ is, for example, 100 to 3000 mPas, preferably 500 to 2500 mPas, more preferably 1000 to 2000 mPas, and further preferably 1200 to 1700 mPas.
(A) The NCO content of the polyisocyanate compound is not particularly limited, but is, for example, 15 to 45%, more preferably 20 to 40%, and still more preferably 20 to 35%.
From the viewpoint of further improving heat resistance and hydrolysis resistance, the polyisocyanate compound (a) preferably includes: (Aa-1) isocyanurate bodies of polyisocyanate compounds (more preferably (A1a-1) isocyanurate bodies of aliphatic polyisocyanate compounds), (a2) alicyclic polyisocyanate compounds (more preferably hydrogenated products of 4,4 '-diphenylmethane diisocyanate), (A3) aromatic polyisocyanate compounds (polyisocyanates having carbodiimide groups derived from 4, 4' -diphenylmethane diisocyanate (carbodiimide-modified MDI)), and the like.
Among them, preferred commercially available products of the polyisocyanate compound (a) include, for example: DURANATE (registered trademark) TPA-100 (manufactured by Asahi Kasei Chemicals), LUPRANATE (registered trademark) M5S (manufactured by BASF INOAC Polyurethanes), WANNATE (registered trademark) HMDI (hydrogenated MDI, manufactured by Wanhua chemical Japan K.K.), MILLIONATE (registered trademark) MTL (manufactured by Tosoh Corp.), and the like.
(A) The polyisocyanate compound may be used alone or in combination of two or more thereof.
Among these compounds, it is preferable to use two compounds as the polyisocyanate compound (A), and it is more preferable to use a mixture of the isocyanurate body of the polyisocyanate compound (Aa-1) and the alicyclic polyisocyanate compound (A2), and it is further preferable to use a mixture of the isocyanurate body of the aliphatic polyisocyanate compound (A1a-1) and the hydride of 4, 4' -diphenylmethane diisocyanate (A2).
The content of the polyisocyanate compound (a) is not particularly limited as long as it is an amount that can be used in a polyurethane resin composition (particularly, a polyurethane resin composition for sealing electric and electronic components). The content is, for example, usually 0.01 to 25% by mass, preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, and particularly preferably 1.5 to 6% by mass, based on 100% by mass of the polyurethane resin composition.
The content of the polyisocyanate compound (A) is, for example, 5 to 75 parts by mass, preferably 8 to 65 parts by mass, and more preferably 10 to 60 parts by mass, based on 100 parts by mass of the polyol compound (B).
In the polyurethane resin composition of the present invention, when two or more kinds of the polyisocyanate compounds (a) are blended, the total amount thereof can be adjusted according to the content of the polyisocyanate compound (a) described above. For example, when the isocyanurate of the (Aa-1) polyisocyanate compound and the (A2) alicyclic polyisocyanate compound are blended as the (A) polyisocyanate compound, the content of the isocyanurate of the (Aa-1) polyisocyanate compound is usually 1 to 400 parts by mass, preferably 10 to 380 parts by mass, and more preferably 100 to 350 parts by mass, based on 100 parts by mass of the (A2) alicyclic polyisocyanate compound.
When the (a3) aromatic polyisocyanate compound is contained in the polyurethane resin composition of the present invention, the content thereof is usually 0.01 to 25% by mass, preferably 1 to 10% by mass, and more preferably 2 to 4% by mass, based on 100% by mass of the polyurethane resin composition.
The amount of the polyisocyanate compound (a) and the polyol compound (B) is such that the NCO/OH ratio (INDEX), which is the ratio of the number of moles of isocyanate groups in the polyisocyanate compound to the number of moles of the total hydroxyl groups in the polyol compound, is 0.5 to 1.5, preferably 0.7 to 1.3, and more preferably 0.8 to 1.1.
When the isocyanurate compound containing the (Aa) polyisocyanate compound (more preferably the isocyanurate compound of the (A1a-1) aliphatic polyisocyanate compound) is used as the (a) polyisocyanate compound, the content thereof is usually 1 to 80 parts by mass, preferably 10 to 80 parts by mass, more preferably 30 to 80 parts by mass, and still more preferably 50 to 80 parts by mass, based on 100 parts by mass of the (a) polyisocyanate compound, from the viewpoint of further improving the heat resistance and hydrolysis resistance.
In the case where the (a) polyisocyanate compound further contains a core of the (Ab) polyisocyanate compound (preferably a core of the (A3b) aromatic polyisocyanate compound) in addition to the isocyanurate body of the (Aa-1) polyisocyanate compound (more preferably an isocyanurate body of the (A1a-1) aliphatic polyisocyanate compound), or in the case where the (Ab) polyisocyanate compound further contains a core of the (Ab) polyisocyanate compound (preferably a core of the (A3b) aromatic polyisocyanate compound) and a carbodiimide body of the (Aa-2) polyisocyanate compound (preferably a carbodiimide body of the (A3a-2) aromatic polyisocyanate compound), from the viewpoint of further improving the electrical characteristics, the amount of the (Aa-1) polyisocyanate compound is 100 parts by mass, the content of (Ab) and/or (Aa-2) is, for example, 1 to 1000 parts by mass, preferably 5 to 800 parts by mass, more preferably 8 to 700 parts by mass, and still more preferably 65 to 500 parts by mass.
1-2.(B) polyol compound
The polyol compound (B) used in the present invention contains (B1) a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less (hereinafter, also referred to as "(B1) polybutadiene polyol"). The polyol compound (B) is a compound different from a crosslinking agent or a plasticizer described later. That is, (B) the polyol compound does not contain an alcohol compound in the crosslinking agent or the plasticizer. As the polyol compound (B), a polyol compound not containing castor oil or castor oil can be selected.
Commercially available products of polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less (b1) include, for example: polybutadiene polyol [ NISSO-PBG series (G-1000, G-2000, G-3000, etc.), "Poly Bd (registered trademark) series (R-45M, R-45HT, CS-15, CN-15, etc.) ] manufactured by Nippon Caoda corporation, Japan, and the like ].
The hydroxyl value of the polybutadiene polyol (b1) is preferably 1 to 58mgKOH/g, more preferably 5 to 55mgKOH/g, and particularly preferably 10 to 50 mgKOH/g.
The hydroxyl group content of the polybutadiene polyol (b1) is not particularly limited, but is usually 0.001 to 3mol/kg, preferably 0.01 to 2mol/kg, and more preferably 0.1 to 1.2 mol/kg.
(b1) The number average molecular weight (Mn) of the polybutadiene polyol is usually in the range of 100 to 5000, preferably 1000 to 4000, and more preferably 1500 to 3500.
The polybutadiene polyol (b1) has a viscosity (30 ℃) of usually 0.01 to 100 pas, preferably 0.1 to 100 pas, and more preferably 1 to 10 pas.
The iodine value of the polybutadiene polyol (b1) is usually in the range of 1 to 1000g/100g, preferably 10 to 600 pas, and more preferably 100 to 500 pas.
The polybutadiene polyol (b1) having a hydroxyl value of 60mgKOH/g or less may be used singly or in combination of two or more.
The polyol compound (B) used in the present invention may further contain a polyol compound (B2) (hereinafter referred to as "polyol B2") having one or more hydroxyl groups, in addition to the polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less.
Examples of the (b2) polyol include: dimer acid polyol; castor oil polyols; polydiene polyols (polyisoprene polyols and the like); a polyether polyol; a polyester polyol; a polycarbonate polyol; a polycaprolactone polyol; an acrylic polyol; and hydrides thereof (for example, hydrides of polydiene polyols, etc.).
The dimer acid polyol is not particularly limited, and a known dimer acid polyol can be used.
The castor oil-based polyol is not particularly limited, and examples thereof include castor oil and castor oil derivatives.
Examples of the castor oil derivative include: castor oil fatty acids; hydrogenated castor oil obtained by hydrogenating castor oil or castor oil fatty acid; transesterifications of castor oil with other fats and oils; a reactant of castor oil and a polyol; esterification reactants of castor oil fatty acids with polyols; and compounds obtained by addition polymerization of alkylene oxides to these compounds. Among the above castor oil-based polyols, castor oil is preferably used.
Examples of the hydrogenated castor oil include those disclosed in Japanese patent application laid-open No. 2-298574. Hydrogenated castor oil can be obtained by hydrogenating the above castor oil polyol.
The number average molecular weight (Mn) of the castor oil polyol is usually in the range of 100 to 4000, preferably in the range of 300 to 2500.
The average hydroxyl value of the castor oil polyol is preferably 20 to 250mgKOH/g, more preferably 50 to 120mgKOH/g, as determined in accordance with JIS K1557-1.
In the present specification, the number average molecular weight (Mn) can be measured by a Gel Permeation Chromatography (GPC) method (polystyrene conversion). Specifically, Shodex GPC 21 manufactured by Showa Denko K.K. was used as a measuring apparatus, Shodex LF-804/KF-803/KF-804 manufactured by Showa Denko K.K. was used as a column, NMP was used as a mobile phase, and the number average molecular weight by GPC was calculated using a calibration curve of standard polystyrene.
The polydiene polyol is not particularly limited, and examples thereof include polyisoprene polyol ("Poly ip" manufactured by shinning corporation) and the like.
The hydrogenated product of the polydiene polyol is not particularly limited, and examples thereof include: hydrogenated products of polybutadiene polyols ("NISSO-PBGI series" manufactured by Nippon Caoda corporation (GI-1000, GI-2000, GI-3000, etc.)), hydrogenated products of polyisoprene polyols ("EPOL" manufactured by Kaisha corporation), and the like.
The polyether polyol is not particularly limited, and examples thereof include polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide using water, low-molecular polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and the like), bisphenols (bisphenol a and the like), dihydroxybenzenes (catechol, resorcinol, hydroquinone, and the like), and the like as an initiator. Specific examples thereof include polyethylene glycol, polypropylene glycol, and polybutylene glycol.
The polyester polyol is not particularly limited, and can be obtained by, for example, an esterification reaction of a polyol component and an acid component.
The polyol component is not particularly limited, and examples thereof include: ethylene glycol, diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, 1, 8-decanediol, octadecanediol, glycerol, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol, and the like.
The acid component is not particularly limited, and examples thereof include: succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1, 12-dodecanedioic acid, 1, 14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1, 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 4' -biphenyldicarboxylic acid, anhydrides thereof, and the like.
The polycarbonate polyol is not particularly limited, and examples thereof include: a polycarbonate polyol obtained by subjecting the polyol component and phosgene to a polycondensation reaction; polycarbonate polyols obtained by subjecting the above polyol component to ester exchange condensation with a carbonic acid diester such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, or dibenzyl carbonate; a copolymerized polycarbonate polyol obtained by using two or more of the above polyol components; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and a carboxyl group-containing compound to an esterification reaction; polycarbonate polyols obtained by etherification of the above-mentioned various polycarbonate polyols with a hydroxyl group-containing compound; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and an ester compound to an ester exchange reaction; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and a hydroxyl group-containing compound to an ester exchange reaction; polyester polycarbonate polyols obtained by polycondensation of the above polycarbonate polyols with dicarboxylic acid compounds; and a copolymerized polyether polycarbonate polyol obtained by copolymerizing the above-mentioned various polycarbonate polyols with alkylene oxide.
The polycaprolactone polyol is not particularly limited, and examples thereof include caprolactone-based polyesterdiols obtained by ring-opening polymerization of cyclic ester monomers such as e-caprolactone and δ -valerolactone.
Examples of the acrylic polyol include copolymers obtained by copolymerizing a hydroxyl group-containing acrylate with a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylate.
Examples of the hydroxyl group-containing acrylate include: 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-dihydroxymethylbutyl (meth) acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, and the like. 2-hydroxyethyl (meth) acrylate and the like are preferable.
Examples of the copolymerizable vinyl monomer include: alkyl (meth) acrylates (having 1 to 12 carbon atoms) such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl acrylate;
for example, aromatic vinyl monomers such as styrene, vinyl toluene and α -methylstyrene;
vinyl cyanide monomers such as (meth) acrylonitrile;
for example, a vinyl monomer containing a carboxyl group such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, or an alkyl ester thereof;
alkane polyol poly (meth) acrylates such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolpropane tri (meth) acrylate;
for example, an isocyanate group-containing vinyl monomer such as 3- (2-isocyanato-2-propyl) - α -methylstyrene, and the like.
The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylate and copolymerizable vinyl monomer in the presence of an appropriate solvent and a polymerization initiator.
The acrylic polyol includes, for example, silicone polyol, fluorine polyol, and the like.
Examples of the silicone polyol include: an acrylic polyol obtained by blending a vinyl group-containing organosilicon compound such as γ -methacryloxypropyltrimethoxysilane as a copolymerizable vinyl monomer in the copolymerization of the acrylic polyol, and the like.
Examples of the fluoropolyol include: in the copolymerization of the acrylic polyol, for example, an acrylic polyol obtained by blending a fluorine compound containing a vinyl group such as tetrafluoroethylene or chlorotrifluoroethylene as a copolymerizable vinyl monomer is used.
The vinyl monomer-modified polyol can be obtained by reacting the above-mentioned high molecular weight polyol with a vinyl monomer.
The polyol compound (B) used in the present invention may be (B1) a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less, or (B1) a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less and a hydroxyl group-containing compound (B2) other than the polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less. As the polybutadiene polyol (b1), two or more kinds of polybutadiene polyols having different molecular weights can be used. Two or more hydroxyl group-containing compounds (b2) other than the polybutadiene polyol can also be used in combination.
The polyurethane resin composition of the present invention can improve the moisture resistance and thermal cycle properties of the polyurethane resin composition by containing the polybutadiene polyol (B-1) as a hydroxyl group-containing compound.
The content of the polybutadiene polyol (b1) used in the present invention is not particularly limited, and is usually 0.01 to 25 mass%, preferably 1 to 20 mass%, and more preferably 5 to 15 mass% with respect to 100 mass% of the polyurethane resin composition.
1-3.(C) inorganic filler
The polyurethane resin composition of the present invention comprises (C) an inorganic filler.
The inorganic filler (C) used in the present invention is not particularly limited, and examples thereof include: metal hydroxides, metal oxides, metal nitrides, zeolites, and the like.
Examples of the metal hydroxide include: aluminum hydroxide, magnesium hydroxide, and the like.
Examples of the metal oxide include: alumina (aluminum oxide), magnesium oxide, silicon oxide (silicon dioxide, etc.), titanium oxide, and the like.
Examples of the metal nitride include: boron nitride, aluminum nitride, silicon nitride, and the like.
The zeolite is not particularly limited, and those used in known polyurethane resin compositions can be used.
Among them, the zeolite is preferably a crystalline aqueous aluminosilicate of an alkali metal or an alkaline earth metal.
The crystal form of the zeolite is not particularly limited, and examples thereof include: type A, type X, type LSX, etc. Among them, the preferred crystal form is form a.
The alkali metal or alkaline earth metal in the zeolite is not particularly limited, and examples thereof include: potassium, sodium, calcium, lithium, and the like. Among them, potassium is preferable.
Preferred inorganic fillers are metal hydroxides and metal oxides, more preferably aluminum hydroxide and aluminum oxide, and particularly preferably aluminum hydroxide.
The inorganic filler (C) may be used singly or in combination of two or more.
The content of the inorganic filler (C) is usually 50 to 85 mass%, preferably 52 to 75 mass%, more preferably 54 to 70 mass%, and particularly preferably 55 to 69 mass% with respect to 100 mass% of the polyurethane resin composition.
(C) The shape of the inorganic filler may be any of a spherical shape and an irregular shape.
1-4.(D) plasticizers
The polyurethane resin composition of the present invention comprises (D) a plasticizer.
The plasticizer (D) used in the present invention is not particularly limited, and examples thereof include: phthalate plasticizers such as dioctyl phthalate, diisononyl phthalate (diisononyl phthalate), and diundecyl phthalate; adipate plasticizers such as dioctyl adipate, diisononyl adipate and diisodecyl adipate; castor oil plasticizers such as methylacetyl ricinoleate, butylacetyl ricinoleate, acetylated triglyceride ricinoleate, acetylated polyglycerol triglyceride oleate, and the like; trimellitic esters such as trioctyl trimellitate and triisononyl trimellitate; and pyromellitic acid ester plasticizers such as tetraoctyl pyromellitate and tetraisononyl pyromellitate.
As the plasticizer (D), a plasticizer not containing an ester compound represented by the following general formula (1) can be selected:
Figure BDA0002615244380000191
in the formula (1), R1And R2Each independently represents an alkyl group having 6 to 12 carbon atoms, and X represents an alkylene group having 3 to 8 carbon atoms. And a and b each independently represent an integer of 2 to 10, and the total of a and b is 4 to 20.
Among the plasticizers (D), phthalate-based plasticizers and adipate-based plasticizers are preferable, and adipate-based plasticizers are more preferable.
The content of the plasticizer (D) is usually 1 to 30% by mass, preferably 10 to 29% by mass, more preferably 12 to 28% by mass, and particularly preferably 15 to 26% by mass, based on 100% by mass of the polyurethane resin composition.
The plasticizer (D) may be used singly or in combination of two or more.
(E) crosslinking agent (chain extender)
The polyurethane resin composition of the present invention may further comprise (E) a crosslinking agent (also known as a chain extender).
The crosslinking agent (E) is not particularly limited, and examples thereof include (E1) alcohol crosslinking agents, (E2) amine crosslinking agents, and the like.
Examples of the (E1) alcohol crosslinking agent include: (E1-1) aromatic alcohol crosslinking agents such as N, N-bis (2-hydroxypropyl) aniline, hydroquinone-bis (. beta. -hydroxyethyl) ether, and resorcinol-bis (. beta. -hydroxyethyl) ether; and (E1-2) aliphatic alcohol crosslinking agents such as ethylene glycol, 1, 4-butanediol, octanediol, trimethylolpropane and triisopropanolamine.
Examples of the (E2) amine-based crosslinking agent include: (E2-1) aromatic amine crosslinking agents such as phenylenediamine, tolylenediamine, diphenyldiamine, 4 ' -diaminodiphenylmethane, 3 ' -bicyclo-4, 4 ' -diaminodiphenylmethane, 1, 2-bis (2-aminophenylthio) ethane, and propylene glycol p-aminobenzoate; and (E2-2) aliphatic amine crosslinking agents such as ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, etc.
Among them, (E1-1) an aromatic alcohol crosslinking agent and (E1-2) an aliphatic alcohol crosslinking agent are preferable, and (E1-1) an aromatic alcohol crosslinking agent is more preferable.
The crosslinking agent (E) has a number average molecular weight of usually 1000 or less, preferably 500 or less, and more preferably 400 or less.
When the urethane resin composition of the present invention contains the crosslinking agent (E), the content of the crosslinking agent (E) is not particularly limited, and is, for example, usually 0.01 to 30% by mass, preferably 0.1 to 20% by mass, more preferably 0.3 to 10% by mass, and particularly preferably 0.5 to 5% by mass, based on 100% by mass of the urethane resin composition.
The crosslinking agent (E) may be used singly or in combination of two or more.
1-6.(F) antifoaming agent
The polyurethane resin composition of the present invention may further contain (F) an antifoaming agent, as necessary.
The defoaming agent used in the present invention is not particularly limited, and examples thereof include: silicones (oil type, complex type, self-emulsifying type, emulsion type, etc.), alcohols, and the like.
The preferred silicone defoaming agent is a modified silicone defoaming agent (in particular, a modified silicone defoaming agent having a polysiloxane as a lipophilic group and modified with a hydrophilic group).
The defoaming agent (F) may be used singly or in combination of two or more.
When the (F) defoaming agent is contained, the content is not particularly limited, but is preferably 0.001 to 10% by mass, and more preferably 0.005 to 5% by mass, based on 100% by mass of the polyurethane resin composition.
1-7 (G) polymerization catalyst
The polyurethane resin composition of the present invention may further contain (G) a polymerization catalyst, if necessary.
As the polymerization catalyst (G), known polymerization catalysts can be used, and examples thereof include: metal catalysts such as organotin catalysts, organolead catalysts, organobismuth catalysts, etc.; amine catalysts, and the like.
Examples of the organotin catalyst include: dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin diacetate, and the like.
Examples of the organolead catalyst include: lead octoate, lead octenoate, lead naphthenate, and the like.
Examples of the organobismuth catalyst include: bismuth octoate, bismuth neodecanoate, and the like.
Examples of the amine catalyst include: diethylenetriamine, triethylamine, N-dimethylcyclohexylamine, N '-tetramethylethylenediamine, N', N "-pentamethyldiethylenetriamine, trimethylenediamine, dimethylaminoethanol, bis (2-dimethylaminoethyl) ether and the like. As the catalyst, an organometallic compound, a metal complex compound, or the like can be used.
When the polymerization catalyst (G) is contained, the content thereof is not particularly limited, and is, for example, usually 0.00001 to 10 mass%, preferably 0.0001 to 5 mass%, and more preferably 0.001 to 1 mass% with respect to 100 mass% of the polyurethane resin composition.
The polymerization catalyst (G) may be used singly or in combination of two or more.
1-8. other ingredients
The polyurethane resin composition of the present invention may further contain various additives such as an antioxidant, a tackifier, a curing accelerator, a colorant, a chain extender, a crosslinking agent, a filler, a pigment, a filler, a flame retardant, a urethane-forming catalyst, an ultraviolet absorber, a moisture absorbent, a mold inhibitor, a silane coupling agent, and the like, as required.
The content of these components may be determined appropriately within the same range as the usual amount of addition depending on the purpose of use so as not to impair the desired characteristics of the polyurethane resin composition.
The polyurethane resin composition of the present invention does not contain a foaming agent. That is, the polyurethane resin composition of the present invention is intended to emit heat or the like by the inorganic filler, whereas the polyurethane foam containing the foaming agent is intended to insulate heat or the like, and therefore, the purposes of the two are different.
2. Method for producing polyurethane resin composition
The method for producing the polyurethane resin composition of the present invention is not particularly limited, and the polyurethane resin composition can be produced by a known method used as a method for producing a polyurethane resin composition.
Examples of such a production method include a method including the following steps: the production process comprises the steps of (1) preparing a composition (first component) containing (A) a polyisocyanate compound, (2) preparing a composition (second component) containing (B) a polyol compound, and (3) mixing the second component with the first component to obtain a polyurethane resin composition.
If the first component (agent I) contains (A) a polyisocyanate compound and the second component (agent II) contains (B) a polyol compound, other components may be contained in either the second component or the first component.
Here, the first component (agent I) may contain other components in addition to the polyisocyanate compound (a).
The second component (agent II) may contain other components in addition to the polyol compound (B).
For example, in the case where the polyol compound is contained as the first component (agent I) in addition to the polyisocyanate compound (a), the first component (agent I) may be a urethane prepolymer having an isocyanate group (NCO) at the end.
Similarly, in the case where (a) the polyisocyanate compound is contained as the second component (agent II) in addition to the polyol compound (B), the second component (agent II) may be a urethane prepolymer having a hydroxyl group (OH) at the end.
Specifically, the urethane prepolymer (X) is obtained by reacting components including (a) a polyisocyanate compound and (B) a polyol compound. The urethane prepolymer (X) may be a urethane prepolymer obtained by reacting not only a material composed of the components (a) and (B) but also a material composed of the components (a) and (B), a crosslinking agent (E), an optional component, and the like, and may be a urethane prepolymer containing other components.
More specifically, the polyurethane resin composition of the present invention includes, for example, the following: a first component containing (A) a polyisocyanate compound and (D) a plasticizer, and a second component containing (B) a polyol compound and (C) an inorganic filler; a first component containing (A) a polyisocyanate compound and a second component containing (B) a polyol compound, (C) an inorganic filler and (D) a plasticizer; the first component contains (A) a polyisocyanate compound and (D) a plasticizer, and the second component contains (B) a polyol compound, (C) an inorganic filler and (D) a plasticizer.
Further, the following configuration may be adopted:
a first component containing (A) a polyisocyanate compound and (C) an inorganic filler, and a second component containing (B) a polyol compound;
a first component containing (A) a polyisocyanate compound and (D) a plasticizer, and a second component containing (B) a polyol compound, (C) an inorganic filler, (D) a plasticizer and (E) a crosslinking agent;
a first component containing (A) a polyisocyanate compound and (D) a plasticizer, and a second component containing (B) a polyol compound, (C) an inorganic filler, (D) a plasticizer, (E) a crosslinking agent, and (F) an antifoaming agent;
the first component contains (A) a polyisocyanate compound and (D) a plasticizer, and the second component contains (B) a polyol compound, (C) an inorganic filler, (D) a plasticizer, (E) a crosslinking agent, (F) an antifoaming agent, and (G) a polymerization catalyst.
In the production of the polyurethane resin composition, the first component (agent I) is usually 1 to 1000 parts by mass, preferably 3 to 100 parts by mass, and more preferably 5 to 25 parts by mass, based on 100 parts by mass of the second component (agent II).
The other components are added to the first component in order to reduce the viscosity of the polyisocyanate compound and to match the ratio (mixing ratio) of the first component to the second component. Therefore, the first component may be used without adding another component thereto.
In the polyurethane resin composition, (a) the polyisocyanate compound and (B) the polyol compound may be partially or completely reacted to form a polyurethane resin. That is, the polyurethane resin composition may be in a liquid state before curing, or may be cured. Examples of the method for curing the polyurethane resin composition include the following methods: the polyurethane resin composition may be cured with time or cured by heating by mixing the first component and the second component to react the polyisocyanate compound (a) with the polyol compound (B) to form a polyurethane resin. In this case, the heating temperature is preferably about 40 to 120 ℃, and the heating time is preferably about 0.5 to 24 hours.
3. Use of
The present invention also provides a sealing material comprising the polyurethane resin composition. The sealing material comprising the polyurethane resin composition is excellent in heat dissipation, hydrolysis resistance and flame retardancy, and can be suitably used for electric and electronic parts, semiconductors and the like which generate heat because the decrease in flame retardancy is suppressed even when used in a high-temperature environment.
Examples of such electrical and electronic components include: transformers such as transformer coils, choke coils, and reactor coils, equipment consoles, and various sensors. Such an electric and electronic component is also one of the present invention. The electric and electronic parts of the present invention can be used for, for example, electric washing machines, toilet bowls, water heaters, water purifiers, bath apparatuses, dish washers, electric tools, automobiles, motorcycles, and the like.
Examples
The polyurethane resin composition of the present invention will be specifically described below with reference to examples and comparative examples. However, the examples are only examples, and the present invention is not limited to the examples.
The raw materials used in examples and comparative examples are shown below.
< polyisocyanate Compound (A) >
a1：TPA-100
Trade name: DURANATE (registered trademark) TPA-100(HDI isocyanurate modifier), manufactured by Asahi Chemicals Ltd
a2：HMDI
Trade name: WANNATE (registered trademark) HMDI (hydrogenated MDI) manufactured by Wanhua chemical Japan K.K
a3：MTL
Trade name: MILLIONATE (registered trademark) MTL (carbodiimide-modified MDI), manufactured by Tosoh corporation
< polyol Compound (B) >
b1：R-45HT
Trade name: poly bd (registered trademark) R-45HT, available from gloss petrochemicals, number average molecular weight 2800, hydroxyl value 46.6mg KOH/g (JIS K1557), hydroxyl group content 0.83mol/kg (JIS K1557), iodine value 398g/100g (JIS K0070), viscosity 5 Pa.S/30 ℃ (JIS K2283)
b2 (comparative polyol compound): r-15HT
Trade name: poly bd (registered trademark) R-15HT, available from gloss petrochemicals, number average molecular weight 1200, hydroxyl value 102.7mg KOH/g (JIS K1557), hydroxyl group content 1.83mol/kg (JIS K1557), iodine value 420g/100g (JIS K0070), viscosity 1.5 Pa.S/30 ℃ (JIS K2283)
< inorganic Filler >
c1：H-32
Trade name: HYDILITEH (registered trademark) H-32 (aluminum hydroxide), manufactured by Showa Denko K.K
< plasticizer (D) >
d 1: diisodecyl Adipate (DIDA)
Trade name: DIDANB, manufactured by TIAOKANG CHEMICAL INDUSTRIAL CO., LTD
d 2: diundecyl phthalate (DUP)
Trade name: DUP, manufactured by J-PLUS
< crosslinking agent (E) >
e 1: OK alcohol 100(OK オール 100): trade name of Uzugaku Kogyo Co., Ltd., molecular weight 212
e 1: octanediol: trade name of KH NEOCHEM, molecular weight 145
< F > defoaming agent
f1：SC-5570
Trade name: SC-5570 (Silicone antifoaming agent), manufactured by Toronto Kangning Co., Ltd
< polymerization catalyst >
g1：U-810
Trade name: neostann U-810 (dioctyltin dilaurate), manufactured by Nidokyo Kaisha
[ preparation of polyurethane resin composition ]
(examples 1 to 11 and comparative examples 1 to 6)
Each of the polyurethane resin compositions was prepared by mixing the components and 0.01 wt% of SC-5570 (silicone defoamer) as a defoamer in the composition shown in table 1, according to the following procedure.
The polyol compound (B), the inorganic filler (C), the plasticizer (D), the crosslinking agent (E), the defoaming agent (F) and the polymerization catalyst (G) shown in table 1 were mixed at 2000rpm using a rotation/revolution mixer (zawa, manufactured by THINKY corporation) for 1 minute.
To the above-mentioned mixed components, (a) a polyisocyanate compound shown in table 1 was added, and the mixture was mixed for 1 minute at 2000rpm using a rotation/revolution mixer (zawa, manufactured by THINKY corporation). The resulting mixture was degassed to obtain the polyurethane resin compositions of examples 1 to 11 and comparative examples 1 to 6.
< preparation of test piece (test piece) >
The prepared polyurethane resin composition was injected into a molding die of 130X 3mm or a molding die of 30mm in inner diameter, 10mm in height and 10X 80X 3mm in height. Subsequently, the polyurethane resin composition was heated at 60 ℃ for 16 hours and then left to cure at room temperature for 1 day to obtain a test piece A (130X 3mm), a test piece B (30 mm in diameter and 10mm in height), and a test piece C (10X 80X 3 mm).
The test piece A was prepared into a No. 3 dumbbell test piece D according to JIS K6251, and a tensile test was carried out using the test piece at a measurement temperature of 25 ℃ and a tensile speed of 500 mm/min by the method specified in item 3 of JIS K6251 to measure the elongation (flexibility). The results are shown in table 1.
The hardness, compatibility, workability, heat resistance, elastic modulus (DMA method: 10Hz), and volume resistance of the obtained test piece A (130X 3mm), test piece B (diameter 30mm and height 10mm), and/or test piece C (10X 80X 3mm) were measured by the following test methods. The results are shown in table 1.
< hardness >
According to JIS K6253, the hardness (type A) of test specimen B (the above-mentioned cured product B, inner diameter 30mm, height 10mm) at 23 ℃ was measured using a durometer (ASKER rubber durometer type A, manufactured by Polymer instruments Co.).
< compatibility (overview) >
The liquid mixture of the polyol compound, the crosslinking agent, the plasticizer, the antifoaming agent, the inorganic filler and the polymerization catalyst was heated for 1 week by a dryer at 60 ℃ and cooled to room temperature (23 ℃) to confirm the overview. Compatibility (overview) was evaluated according to the following evaluation criteria.
A: the upper layer (supernatant) of the mixture was free of a clear layer (phase separation);
c: the upper layer (supernatant) of the mixture was clear (phase separation).
< workability (flowability) >
A container containing a mixed liquid of polyisocyanate, a polyol compound, a crosslinking agent, a plasticizer, an antifoaming agent, an inorganic filler and a polymerization catalyst was tilted and poured by natural dropping into a molding die of 130X 3mm or a molding die of 30mm in inner diameter and 10mm in height, 10X 80X 3mm, to confirm fluidity. Workability (fluidity) was evaluated according to the following evaluation criteria.
A: the mixed liquid material is completely diffused in accordance with the shape of the molding die.
C: the mixed liquid material does not spread in accordance with the shape of the molding die.
< Heat resistance >
After the initial hardness was measured, the test piece B was heated by a drier at 100 ℃ for 500 hours, cooled to room temperature (23 ℃), and then the hardness (final hardness) of the test piece was measured in the same manner as the initial hardness. The hardness change rate was calculated from the initial hardness and the final hardness based on the following formula.
Formula (II): hardness change rate (%) - (final hardness-initial hardness)/initial hardness ] × 100
Based on the calculated hardness change rate, the heat resistance was evaluated according to the following evaluation criteria.
A: the hardness change rate is lower than 30 percent;
b: a hardness change rate of 30% or more and less than 40%;
c: the hardness change rate is 40% or more.
< elongation (flexibility) >
The elongation (flexibility) of the test piece D was evaluated according to JIS K6251 based on the following formula.
Formula (II): elongation { [ (distance between marking lines at break) - (distance between marking lines) ]/(distance between marking lines) } × 100 { [ (distance between marking lines) }
A: the elongation is more than 100%;
b: an elongation of 80% or more and less than 100;
c: the elongation is less than 80%.
< elastic modulus (10Hz) >
The elastic modulus (10Hz) of the test piece C was measured using a dynamic viscoelastometer DMA (manufactured by SII Nano Technology, DMS 6100). The elastic modulus was evaluated according to the following evaluation criteria.
The value was determined as a pass value when the modulus of elasticity (10Hz) at-40 ℃ was 40MPa or less.
The change in elastic modulus (MPa) of the test piece C was evaluated based on the following formula.
Formula (II): change in elastic modulus (MPa) [ -elastic modulus at 40 deg.C (MPa) ] - [ elastic modulus at 120 deg.C (MPa) ]
The elastic modulus at-40 ℃ to 120 ℃ is changed to 40MPa or less as a qualified value.
Further, the elastic modulus at-40 ℃ to 120 ℃ is changed to 30MPa or less as a good product.
< volume resistance value >
The volume resistivity of the test piece A was measured by using a resistance measuring instrument (manufactured by HIOKI Co., Ltd., DSM-8104). Based on the measurement results, the insulation properties were evaluated according to the following evaluation criteria. The measurement value (Ω · cm) of the volume resistivity and the evaluation result are shown in table 1.
The volume resistivity is 1 x 1012The value is not less than Ω · cm.
In the table, "-" indicates that no data is available because the polyurethane resin cannot be molded.
[ Table 1]
Figure BDA0002615244380000301
< determination result >
From the results of examples 1 to 11, it is understood that the polyurethane resin composition of the present invention can reduce the temperature dependence of the elastic modulus (120 ℃ to-40 ℃), exhibit excellent elongation (flexibility), and can suppress the change in hardness due to thermal deterioration.
Further, it was found that the polyurethane resin composition of the present invention satisfies each of excellent compatibility, workability, hardness and volume resistance value.
On the other hand, it is found that the compositions of comparative examples 1 to 6 do not satisfy each of the temperature dependence of the elastic modulus, the elongation (flexibility), the hardness change due to thermal deterioration, the compatibility, the workability, the hardness, and the volume resistance value.
In examples 1 to 11, the measurement data of the elongation and the elastic modulus after heat resistance at 100 ℃/700 hours of the examples 1,4 and 11 were compared with those of comparative example 4, and are shown in table 2.
[ Table 2]
Figure BDA0002615244380000311
< determination result >
From the results of examples 1,4 and 11, the polyurethane resin composition of the present invention is superior to comparative example 4 in elastic modulus and elongation (flexibility) even after standing at 100 ℃/700 hours, and can suppress the change in hardness due to thermal deterioration.
Industrial applicability
When the polyurethane resin composition of the present invention is used, the resulting polyurethane resin cured product satisfies each of heat resistance, moisture resistance and thermal cyclability, and therefore can be used in the fields of electric products, electronic components and the like.

Claims (13)

1. A polyurethane resin composition comprising (A) a polyisocyanate compound, (B) a polyol compound, (C) an inorganic filler and (D) a plasticizer,
the polyisocyanate compound (A) is an isocyanurate of an aliphatic polyisocyanate compound, an allophanate of an aliphatic polyisocyanate compound, an alicyclic polyisocyanate, and/or an aromatic polyisocyanate,
the polyol compound (B) comprises (B1) a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less,
the (D) plasticizer does not contain an ester compound represented by the general formula (1):
Figure FDA0003044726630000011
in the formula (1), R1And R2Each independently represents an alkyl group having 6 to 12 carbon atoms, X represents an alkylene group having 3 to 8 carbon atoms, a and b each independently represents an integer of 2 to 10, the total of a and b is 4 to 20,
the polyurethane resin composition comprises (b1) 5 to 15% by mass of a polybutadiene polyol having a hydroxyl value of 60mgKOH/g or less, (C) 50 to 85% by mass of an inorganic filler, and (D) 1 to 30% by mass of a plasticizer, based on 100% by mass of the polyurethane resin composition,
the polyurethane resin composition has an elastic modulus of 40MPa or less at-40 ℃ and 10 Hz.
2. The polyurethane resin composition according to claim 1, wherein the number average molecular weight Mn of the polybutadiene polyol (b1) is in the range of 100 to 5000.
3. The polyurethane resin composition according to claim 1 or 2, wherein the viscosity of the polybutadiene polyol (b1) at 30 ℃ is in the range of 0.01 to 100 Pa-s.
4. The polyurethane resin composition according to claim 1 or 2, wherein the polyurethane resin composition further contains (E) a crosslinking agent.
5. The polyurethane resin composition according to claim 4, wherein the (E) crosslinking agent is (E1) an aromatic alcohol crosslinking agent and/or (E2) an aliphatic alcohol crosslinking agent.
6. The polyurethane resin composition according to claim 4, wherein the (E) crosslinking agent is (E1) an aromatic alcohol crosslinking agent.
7. The polyurethane resin composition according to claim 4, wherein the crosslinking agent (E) is a crosslinking agent having a number average molecular weight of 400 or less.
8. The polyurethane resin composition according to claim 1 or 2, wherein the (D) plasticizer comprises (D1) an adipic acid-based plasticizer and/or (D2) a phthalic acid-based plasticizer.
9. The polyurethane resin composition according to claim 1 or 2, wherein the (D) plasticizer is (D1) an adipic acid-based plasticizer.
10. The polyurethane resin composition according to claim 1 or 2, wherein the plasticizer (D) is contained in an amount of 10 to 29% by mass based on 100% by mass of the polyurethane resin composition.
11. The urethane resin composition according to claim 1 or 2, wherein the urethane resin composition is used for sealing an electric and electronic part.
12. A sealing material comprising the polyurethane resin composition according to any one of claims 1 to 11.
13. An electric/electronic component, wherein the electric/electronic component is resin-sealed with the sealing material according to claim 12.
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