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CN116368006B - Polyisocyanate composition, cured film, coating film, adhesive composition, adhesive sheet and resin composition - Google Patents

Polyisocyanate composition, cured film, coating film, adhesive composition, adhesive sheet and resin composition Download PDF

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Publication number
CN116368006B
CN116368006B CN202180074314.4A CN202180074314A CN116368006B CN 116368006 B CN116368006 B CN 116368006B CN 202180074314 A CN202180074314 A CN 202180074314A CN 116368006 B CN116368006 B CN 116368006B
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polyol
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polyisocyanate composition
film
mass
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CN116368006A (en
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东昌嗣
武井丽
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Asahi Kasei Corp
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Asahi Kasei Corp
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Priority claimed from JP2020192690A external-priority patent/JP7688966B2/en
Priority claimed from JP2021173926A external-priority patent/JP2022081414A/en
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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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/40—High-molecular-weight compounds
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Disclosed is a polyisocyanate composition derived from at least 1 diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, a 2-functional polyol (A1) having a number average molecular weight of 1500 or more, and a 3-functional polyol (B1) having a number average molecular weight of 500 or more, wherein the molar ratio of the isocyanate groups of the diisocyanate to the hydroxyl groups of the polyol (A1) and the polyol (B1) is 2 or more and 30 or less, and the weight average molecular weight of the polyisocyanate composition is 1400 or more. The present invention also provides a polyisocyanate composition derived from at least 1 diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, a polycaprolactone polyol (A2), and a polyether polyol (B2), and comprising 20 parts by mass or more of polypropylene glycol per 100 parts by mass of the polyether polyol (B2).

Description

Polyisocyanate composition, cured film, coating film, adhesive composition, adhesive sheet, and resin composition
Technical Field
The present invention relates to a polyisocyanate composition, a cured film, a coating film, an adhesive composition and an adhesive sheet. The invention further relates to a polyisocyanate composition and a resin composition.
Background
In recent years, plastic films, adhesives, and adhesives have been used in various fields because of their wide variety of functions. Under such circumstances, not only the application to flat plate-like portions but also the application to portions with low frequency of use in the past such as curved surfaces and portions with bending operations are increasing. For example, there is a rapid increase in demand in recent years, including devices such as flexible displays and foldable displays. Accordingly, films, adhesives, and binders having high flexibility and excellent buckling resistance, which are excellent in following curved surfaces and buckling, have been demanded.
In addition, in order to achieve coating properties which cannot be solved by conventional curing agents, there is an increasing market demand for curing agents with higher quality and higher performance. In particular, for coating films, adhesives, binders, sealants, and the like which exhibit final physical properties by curing, further development is required to better exhibit the performance derived from the curing agent. In particular, as the market moves, there is a tendency that high flexibility is required for the composition after curing.
Patent documents 1 and 2 disclose polyisocyanate compositions modified with polyester polyols or polyether polyols. Disclosed is a coating film which is formed by compounding the composition and has excellent extensibility and buckling resistance.
Prior art literature
Patent literature
Patent document 1 Japanese patent laid-open No. 61-28518
Patent document 2 Japanese patent laid-open No. 2-1718
Disclosure of Invention
Problems to be solved by the invention
There is a demand for a polyisocyanate composition having more excellent flexibility than the polyisocyanate compositions described in patent documents 1 and 2. In patent documents 1 and 2, no specific study is made on the use of adhesives or binders.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyisocyanate composition which gives a cured film having excellent flexibility and excellent adhesion, cohesion, curability and transparency, by curing the polyisocyanate composition alone. Further provided are a cured film, a coating film, an adhesive composition and an adhesive sheet each using the polyisocyanate composition.
In addition, there is a demand for a polyisocyanate composition which can provide a coating film having more excellent flexibility in a severe environment, specifically at a low temperature of about-10 ℃ than the polyisocyanate compositions described in patent documents 1 and 2.
The present invention has been made in view of the above circumstances, and provides a polyisocyanate composition which has excellent compatibility with a main agent in a low-temperature environment of about-10 ℃ and which is excellent in flexibility at a low temperature of about-10 ℃ and at a normal temperature of about 23 ℃ when a coating film is formed. In addition, a resin composition using the aforementioned polyisocyanate composition is provided.
Solution for solving the problem
That is, the present invention includes the following means.
(1) A polyisocyanate composition derived from at least 1 diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, a 2-functional polyol (A1) having a number average molecular weight of 1500 or more, and a 3-functional or higher polyol (B1) having a number average molecular weight of 500 or more,
The molar ratio of isocyanate groups of the diisocyanate to hydroxyl groups of the polyol (A1) and the polyol (B1) is 2 to 30,
The weight average molecular weight of the polyisocyanate composition is 1400 or more.
(2) The polyisocyanate composition according to (1), wherein the mass ratio of the polyol (B1) to the polyol (A1) is 0.1/99.9 or more and 99.9/0.1 or less, and
With respect to 100 parts by mass of the aforementioned diisocyanate,
The content of the polyol (A1) is 0.1 to 250 parts by mass,
The content of the polyol (B1) is 1 to 190 parts by mass.
(3) The polyisocyanate composition according to (1) or (2), wherein the average isocyanate functional group number of the polyisocyanate composition is 2 or more and 6 or less.
(4) The polyisocyanate composition according to any one of (1) to (3), wherein the polyisocyanate composition has an isocyanate group content of 1% by mass or more and 10% by mass or less.
(5) The polyisocyanate composition according to any one of (1) to (4), wherein the polyol (A1) and the polyol (B1) are at least 1 polyol selected from the group consisting of polyester polyols, polyether polyols, epoxy polyols, polyolefin polyols and polycarbonate polyols.
(6) The polyisocyanate composition according to any one of (1) to (5), wherein the polyol (A1) and the polyol (B1) are polyester polyols.
(7) The polyisocyanate composition according to (6), wherein the polyol (A1) and the polyol (B1) are polycaprolactone polyols.
(8) A cured film which is obtained by applying the polyisocyanate composition according to any one of (1) to (7) to glass, storing the film in a humidity environment of 23 ℃ and 65% for 168 hours, heating the film at 50 ℃ for 24 hours, and then forming a cured film having a film thickness of 40 μm,
The cured film has a Ke Nixi hardness of 60 times or less in an environment at 23 ℃.
(9) A coating film which has a film thickness of 40 μm after a coating composition comprising the polyisocyanate composition according to any one of (1) to (7) and an acrylic polyol having a glass transition temperature of 29.1 ℃ and a hydroxyl value of 139mgKOH/g and a weight average molecular weight of 2.56X10 4 is cured at 90 ℃ for 30 minutes and stored at 23 ℃ for 65% humidity,
In a tensile test in which a test piece having a width of 10mm and a length of 100mm of the coating film is set in a tensile tester with a clamp distance of 20mm and measured at a speed of 20 mm/min, the elongation of the coating film is 50% or more and the stress at an elongation of 140% is 28MPa or less.
(10) An adhesive composition comprising the polyisocyanate composition according to any one of (1) to (7) and a crosslinkable functional group-containing polymer having a glass transition temperature of 0 ℃ or less.
(11) The adhesive composition according to (10), wherein the crosslinkable functional group-containing polymer is an acrylic polymer.
(12) An adhesive sheet comprising:
A substrate, and
An adhesive layer on the substrate,
The adhesive layer contains a cured product of the adhesive composition according to (10) or (11).
(13) The adhesive sheet according to (12), wherein the thickness of the adhesive layer is 1 μm or more and 1000 μm or less.
(14) The adhesive sheet according to (12) or (13), wherein the adhesive sheet having an adhesive layer of 50 μm in thickness is obtained by coating the adhesive composition on a release-treated polyethylene terephthalate film of 38 μm in thickness, drying the film at 130 ℃ for 3 minutes, and curing the film, wherein the adhesive sheet is covered with a net-like sheet after storage for 7 days at 23 ℃ in a 50% RH atmosphere, immersed in ethyl acetate for 1 week at 23 ℃, taken out, and dried at 120 ℃ for 2 hours to obtain a gel fraction of 20 mass% or more and 99 mass% or less.
(15) The adhesive sheet according to any one of (12) to (14), wherein the adhesive sheet having a thickness of 50 μm and a width of 20mm and a length of 100mm is obtained by applying the adhesive composition to a polyethylene terephthalate film having a thickness of 50 μm, drying the film at 130℃for 3 minutes and curing the film at 130℃and applying the adhesive composition to a polyethylene terephthalate film having a thickness of 25 μm, and then pressing the film with a SUS304BA steel plate as an adherend by a 2kg roller once and again, curing the film at 23℃for 30 minutes, and then measuring 180 DEG peel adhesion at a speed of 300 mm/min at 23℃for 0.05N/20mm to 55N/20 mm.
(16) The adhesive sheet according to any one of (12) to (15), wherein the adhesive composition is applied to a release-treated polyethylene terephthalate film having a thickness of 38 μm and dried at 130 ℃ for 3 minutes to cure the film, and the release-treated polyethylene terephthalate film is released from the film and then bonded to a glass having a haze value of 0.1% to give an adhesive sheet having a haze value of 2% or less as measured by a haze meter.
(17) A coating film, film and adhesive composition, which is a resin film having a film thickness of 40 μm after curing a resin composition at 90 ℃ for 30 minutes and storing the resin composition in a 23 ℃ and 65% humidity environment for 168 hours, wherein the resin composition comprises the polyisocyanate composition according to any one of (1) to (7) and an acrylic polyol having a glass transition temperature of 0 ℃ to 100 ℃, a hydroxyl value of 10mgKOH/g to 400mgKOH/g, and a weight average molecular weight of 5.00×10 3 to 1.0×10 5,
In a tensile test in which a test piece having a width of 10mm and a length of 100mm of the resin film is set in a tensile tester with a clamp distance of 20mm and measured at a speed of 20 mm/min, the breaking stress of the resin film is 2.0MPa or more.
(18) A coating film, film and adhesive composition, which is a resin film having a film thickness of 40 μm after curing a resin composition at 90 ℃ for 30 minutes and storing the resin composition in a 23 ℃ and 65% humidity environment for 168 hours, wherein the resin composition comprises the polyisocyanate composition according to any one of (1) to (7) and an acrylic polyol having a glass transition temperature of 0 ℃ to 100 ℃, a hydroxyl value of 10mgKOH/g to 400mgKOH/g, and a weight average molecular weight of 5.00×10 3 to 1.0×10 5,
In a tensile test in which a test piece having a width of 10mm and a length of 100mm of the resin film is set in a tensile tester with a clamp distance of 20mm and measured at a speed of 20 mm/min, the breaking stress of the resin film is 1.1 or more with respect to the stress at 140% elongation.
(19) A polyisocyanate composition derived from at least 1 diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, a polycaprolactone polyol (A2), and a polyether polyol (B2),
The polyether polyol (B2) contains polypropylene glycol in an amount of 20 parts by mass or more per 100 parts by mass of the polyether polyol.
(20) The polyisocyanate composition according to (19), wherein the number average molecular weight of the polycaprolactone polyol (A2) is 500 or more and 1500 or less, and
The polyether polyol (B2) has a number average molecular weight of 1000 to 7000.
(21) The polyisocyanate composition according to (20), wherein the mass ratio of polytetramethylene ether glycol to the polypropylene glycol in the polyether polyol (B2) is 0/100 or more and 60/40 or less.
(22) The polyisocyanate composition according to any one of (19) to (21), wherein the molar ratio of isocyanate groups of the diisocyanate to hydroxyl groups of the polycaprolactone polyol (A2) and the polyether polyol (B2) is 2 to 10.
(23) The polyisocyanate composition according to any one of (19) to (22), wherein the mass ratio of the polycaprolactone polyol (A2) to the polyether polyol (B2) is 10/90 or more and 90/10 or less.
(24) A resin composition comprising the polyisocyanate composition according to any one of (19) to (23) and a polyol.
(25) The resin composition according to (24), which is an adhesive composition.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the polyisocyanate composition of the above aspect, it is possible to provide a polyisocyanate composition which gives a cured film having excellent flexibility and excellent adhesion, cohesion, curability and transparency, which is obtained by curing the polyisocyanate composition alone.
In addition, according to the polyisocyanate composition of the above embodiment, it is possible to provide a polyisocyanate composition which is excellent in compatibility with a main agent in a low temperature environment of about-10 ℃ and in flexibility at a low temperature of about-10 ℃ and at a normal temperature of about 23 ℃ when a coating film is formed. The resin composition of the above embodiment contains the polyisocyanate composition and is excellent in flexibility at a low temperature of about-10 ℃ and at a normal temperature of about 23 ℃ when a coating film is formed.
Detailed Description
The mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following. The present invention may be variously modified within a range not departing from the gist thereof.
In the present specification, the term "polyol" refers to a compound having 2 or more hydroxyl groups (-OH) in one molecule.
In the present specification, the term "polyisocyanate" refers to a reaction product obtained by bonding a plurality of monomer compounds having 2 or more isocyanate groups (-NCO).
In addition, in the present specification, "(meth) acrylic acid ester" includes methacrylic acid ester and acrylic acid ester unless otherwise specified.
Polyisocyanate composition 1
The polyisocyanate composition 1 of the present embodiment is derived from a diisocyanate, a 2-functional polyol (A1) having a number average molecular weight of 1500 or more (hereinafter simply referred to as "polyol (A1)") and a 3-functional polyol (B1) having a number average molecular weight of 500 or more (hereinafter simply referred to as "polyol (B1)"). That is, the polyisocyanate composition 1 of the present embodiment is a reaction product of a diisocyanate and the above 2 polyols, and contains a polyisocyanate modified with the above 2 polyols. The diisocyanate is at least 1 selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.
In the polyisocyanate composition 1 of the present embodiment, the molar ratio of isocyanate groups of the diisocyanate to hydroxyl groups of the polyol (A1) and the polyol (B1) (molar ratio of isocyanate groups/hydroxyl groups) is 2 or more and 30 or less, preferably 2.6 or more and 30 or less, more preferably 3 or more and 25 or less, still more preferably 3.5 or more and 24 or less, particularly preferably 5 or more and 23 or less, and most preferably 5 or more and 20 or less.
The molar ratio of isocyanate groups to hydroxyl groups can be calculated, for example, using the molar amount of hydroxyl groups of the polyol (A1) and the polyol (B1) used in the production of the polyisocyanate composition 1 and the molar amount of isocyanate groups of the diisocyanate.
The weight average molecular weight of the polyisocyanate composition 1 of the present embodiment is 1400 or more, preferably 1500 or more.
The upper limit of the weight average molecular weight of the polyisocyanate composition 1 of the present embodiment is not particularly limited, and may be 100000.
The weight average molecular weight of the polyisocyanate composition 1 of the present embodiment can be measured by, for example, gel permeation chromatography (hereinafter, may be abbreviated as "GPC").
The polyisocyanate composition 1 of the present embodiment has the above-described structure, and thus exhibits higher flexibility than conventional ones, and the cured film obtained by curing the polyisocyanate composition 1 alone has good flexibility. In addition, by using the polyisocyanate composition 1 of the present embodiment, an adhesive sheet excellent in adhesion, cohesion, curability and transparency can be obtained.
Next, the details of the components of the polyisocyanate composition 1 according to the present embodiment will be described below.
< Polyisocyanate >
The polyisocyanate composition 1 of the present embodiment may be a polyisocyanate having a structural unit derived from each of the diisocyanate, the polyol (A1) and the polyol (B1) in one molecule, or may be a mixture of polyisocyanates having at least 1 or more structural units derived from the group consisting of the diisocyanate, the polyol (A1) and the polyol (B1) in one molecule.
The polyisocyanate may have at least 1 or more structures selected from the group consisting of an allophanate structure, a uretdione structure, an iminooxadiazinedione structure, an isocyanurate structure, a urea structure, a urethane structure, and a biuret structure. Among them, at least 1 structure selected from the group consisting of a urethane structure, an allophanate structure, a biuret structure, a urea structure, and an isocyanurate group is preferable, and a urethane structure is more preferable.
[ Diisocyanate ]
The diisocyanate is at least 1 selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.
The aliphatic diisocyanate is not limited to the following, and examples thereof include 1, 4-diisocyanatobutane, 1, 5-diisocyanatopentane, ethyl (2, 6-diisocyanato) hexanoate, 1, 6-diisocyanatohexane (hereinafter sometimes abbreviated as "HDI"), 1, 9-diisocyanatononane, 1, 12-diisocyanato dodecane, 2, 4-or 2, 4-trimethyl-1, 6-diisocyanatohexane, and the like. These aliphatic diisocyanates may be used singly or in combination of 2 or more.
Examples of the alicyclic diisocyanate include, but are not limited to, 1, 3-or 1, 4-bis (isocyanatomethyl) cyclohexane (hereinafter, sometimes abbreviated as "hydrogenated XDI"), 1, 3-or 1, 4-diisocyanatocyclohexane, 3, 5-trimethyl 1-isocyanato-3- (isocyanatomethyl) cyclohexane (hereinafter, sometimes abbreviated as "IPDI"), 4-4' -diisocyanato-dicyclohexylmethane (hereinafter, sometimes abbreviated as "hydrogenated MDI"), 2, 5-or 2, 6-diisocyanatomethyl norbornane, and the like. These alicyclic diisocyanates may be used singly or in combination of 2 or more.
These aliphatic diisocyanate and alicyclic diisocyanate may be used alone, the aliphatic diisocyanate and the alicyclic diisocyanate may be used in combination of 2 or more.
From the viewpoint of flexibility, the mass ratio of the alicyclic polyisocyanate to the aliphatic diisocyanate is preferably 0/100 or more and 30/70 or less.
Among them, as the diisocyanate, HDI, IPDI, hydrogenated XDI or hydrogenated MDI is preferable, HDI or IPDI is more preferable, and HDI is further preferable.
In the production of the polyisocyanate, an isocyanate monomer as shown below may be used in addition to the diisocyanate.
(1) Aromatic diisocyanates such as diphenylmethane-4, 4' -diisocyanate (MDI), 1, 5-naphthalene diisocyanate, toluene Diisocyanate (TDI), xylylene diisocyanate, and m-tetramethylxylylene diisocyanate (TMXDI).
(2) Triisocyanates such as 4-isocyanatomethyl-1, 8-octamethylenediisocyanate (hereinafter sometimes referred to as "NTI"), 1,3, 6-hexamethylene triisocyanate (hereinafter sometimes referred to as "HTI"), bis (2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter sometimes referred to as "GTI"), and lysine triisocyanate (hereinafter sometimes referred to as "LTI").
[ Polyol (A1) and polyol (B1) ]
The polyol (A1) is a 2-functional polyol (diol) having a number average molecular weight of 1500 or more.
The polyol (B1) is a polyol having a number average molecular weight of 500 or more and 3 or more functions.
The number average molecular weight of the polyol (A1) is 1500 or more, preferably 1800 or more. When the number average molecular weight of the polyol (A1) is not less than the lower limit, the cured film obtained by curing the polyisocyanate composition alone has low hardness and good flexibility.
On the other hand, the upper limit of the number average molecular weight of the polyol (A1) is not particularly limited, and may be 7000, preferably 6000, more preferably 5000, and even more preferably 4200, for example.
The number average molecular weight Mn of the polyol (A1) is, for example, the number average molecular weight based on polystyrene measured by GPC. When 2 or more polyols (A1) are mixed and used, the number average molecular weight of the mixture is calculated.
The number average molecular weight of the polyol (B1) is 500 or more, preferably 800 or more. When the number average molecular weight of the polyol (B1) is not less than the lower limit, the cured film obtained by curing the polyisocyanate composition alone has low hardness and good flexibility.
On the other hand, the upper limit of the number average molecular weight of the polyol (B1) is not particularly limited, and may be 3000, preferably 2200, more preferably 1500, and even more preferably 1300, for example.
The number average molecular weight Mn of the polyol (B1) is, for example, the number average molecular weight based on polystyrene measured by GPC. When 2 or more polyols (B1) are mixed and used, the number average molecular weight of the mixture is calculated.
The polyol (A1) is preferably at least 1 kind of 2-functional polyol (diol) selected from the group consisting of polyester polyol, polyether polyol, epoxy polyol, polyolefin polyol and polycarbonate polyol, more preferably 2-functional polyester polyol.
Examples of the 2-functional polyester polyol include any of the following (1) and (2). (1) Polyester polyol obtained by condensation reaction of a mixture of 2 or more kinds of dibasic acids and a mixture of 2 or more kinds of dihydric alcohols. (2) And a polycaprolactone polyol obtained by ring-opening polymerization of epsilon-caprolactone with a diol.
Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1, 4-cyclohexanedicarboxylic acid.
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, trimethylpentanediol, and cyclohexanediol.
Among them, 2-functional polyester polyols are preferably 2-functional polycaprolactone polyols.
As the commercially available 2-functional polycaprolactone polyol, for example, trade names "PLACCEL 210" (number average molecular weight 1000, hydroxyl value 112.8mgKOH/g, acid value 0.09 mgKOH/g), "PLACCEL 210CP" (number average molecular weight 1000, hydroxyl value 112.8mgKOH/g, acid value 0.16 mgKOH/g), trade names "PLACCEL 212" (number average molecular weight 1250, hydroxyl value 90.8mgKOH/g, acid value 0.09 mgKOH/g), trade names "PLACCEL 212CP" (number average molecular weight 1250, hydroxyl value 90.2mgKOH/g, acid value 0.14 mgKOH/g), "PLACCEL 220" (number average molecular weight 2000, hydroxyl value 56.7mgKOH/g, acid value 0.06 mgKOH/g), "PLCEL 220B" (number average molecular weight 2000, hydroxyl value 57.2mgKOH/g, 0.16 mgKOH/g), hydroxyl value 0.09mgKOH/g, acid value 0.09mgKOH/g, trade names "PLACCEL 212CP" (number average molecular weight 1250, hydroxyl value 90.2mgKOH/g, acid value 0.14 mgKOH/g), hydroxyl value 220, hydroxyl value 0.7 mgKOH/g, hydroxyl value 0.37, hydroxyl value 0.02 mg/g, hydroxyl value 0.37, hydroxyl value 0.6 mgKOH/g, and so on average molecular weight of the like.
The 2-functional polycaprolactone polyol preferably has a relatively low acid value from the viewpoints of hydrolysis resistance and reaction stability during polyisocyanate synthesis.
The polyol (B1) may be a polyol having 3 or more functions, preferably a polyol having 3 or more functions and 10 or less functions, more preferably a polyol having 3 or more functions and 7 or less functions, still more preferably a polyol having 3 or more functions and 5 or less functions, particularly preferably a polyol having 3 or more functions and 4 or less functions, and most preferably a polyol (triol) having 3 functions.
As the 3-functional polyol (triol), at least 1 kind of 3-functional polyol (triol) selected from the group consisting of polyester polyols, polyether polyols, epoxy polyols, polyolefin polyols and polycarbonate polyols is preferable, and 3-functional polyester polyols are more preferable.
Examples of the 3-functional polyester polyol include any of the following (1) and (2). (1) Polyester polyol obtained by condensation reaction of a mixture of 2 or more kinds of dibasic acid and a mixture of 2 or more kinds of triol. (2) And a polycaprolactone polyol obtained by ring-opening polymerization of epsilon-caprolactone with a triol.
Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1, 4-cyclohexanedicarboxylic acid.
Examples of the triol include trimethylolpropane, glycerol, pentaerythritol, 2-hydroxymethylpropanediol, and ethoxylated trimethylolpropane.
Among them, 3-functional polyester polyols are preferably 3-functional polycaprolactone polyols.
Examples of the commercially available 3-functional polycaprolactone polyols include "PLACCEL 305" (number average molecular weight 550, hydroxyl value 305.6mgKOH/g, acid value 0.50 mgKOH/g), "PLACCEL 308" (number average molecular weight 850, hydroxyl value 195.3mgKOH/g, acid value 0.38 mgKOH/g), "PLACCEL 309" (number average molecular weight 900, hydroxyl value 187.3mgKOH/g, acid value 0.20 mgKOH/g), "PLACCEL 312" (number average molecular weight 1250, hydroxyl value 136.1mgKOH/g, acid value 0.38 mgKOH/g), "PLACCEL 320" (number average molecular weight 2000, hydroxyl value 85.4mgKOH/g, acid value 0.29 mgKOH/g) and the like, which are commercially available from Daxil corporation.
In the polyisocyanate composition 1 of the present embodiment, the mass ratio of the polyol (A1) to the polyol (B1) ((mass ratio of A1)/(B1)) is preferably 0.1/99.9 or more and 99.9/0.1, more preferably 1/99 or more and 99/1 or less, still more preferably 3/97 or more and 90/10 or less, particularly preferably 5/95 or more and 80/20 or less, and most preferably 7/93 or more and 70/30 or less.
When the mass ratio (A1)/(B1) is equal to or greater than the lower limit, the cured film obtained by curing the polyisocyanate composition alone has low hardness and more excellent flexibility. In addition, an adhesive sheet having more excellent adhesiveness and flexibility can be obtained. On the other hand, when the mass ratio of (A1)/(B1) is equal to or less than the above-mentioned upper limit value, an adhesive sheet having more excellent adhesiveness, flexibility and cohesive strength can be obtained.
(A1) The mass ratio/(B1) can be calculated, for example, from the compounding amount of each polyol at the time of producing the polyisocyanate composition 1.
In the polyisocyanate composition 1 of the present embodiment, the content (amount of the polyol (A1) is 0.1 part by mass or more and 250 parts by mass or less, preferably 0.1 part by mass or more and 210 parts by mass or less, more preferably 0.1 part by mass or more and 170 parts by mass or less, still more preferably 0.5 part by mass or more and 100 parts by mass or less, still more preferably 1 part by mass or more and 50 parts by mass or less, still more preferably 1.5 parts by mass or more and 40 parts by mass or less, and particularly preferably 1.7 parts by mass or more and 38 parts by mass or less, per 100 parts by mass of the diisocyanate.
When the content of the polyol (A1) is not less than the lower limit, the cured film obtained by curing the polyisocyanate composition alone has low hardness and more excellent flexibility. In addition, an adhesive sheet having more excellent adhesion and curability can be obtained. On the other hand, when the content of the polyol (A1) is not more than the above-mentioned upper limit, the polyisocyanate composition 1 is produced without gelation, the liquid state can be maintained, and the flexibility is further improved when a resin film is produced.
The content of the polyol (A1) can be calculated, for example, from the amount of the diisocyanate and the polyol (A1) blended in the production of the polyisocyanate composition 1.
In the polyisocyanate composition 1 of the present embodiment, the content (amount of the polyol (B1) is 1 part by mass or more and 190 parts by mass or less, preferably 1 part by mass or more and 140 parts by mass or less, more preferably 1 part by mass or more and 90 parts by mass or less, still more preferably 2 parts by mass or more and 80 parts by mass or less, still more preferably 5 parts by mass or more and 70 parts by mass or less, still more preferably 10 parts by mass or more and 60 parts by mass or less, and particularly preferably 12 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of the diisocyanate.
When the content of the polyol (B1) is not more than the upper limit, the isocyanate composition 1 is produced without gelation, the liquid state can be maintained, and the curability and flexibility are further improved when a resin film is produced. On the other hand, when the content of the polyol (B1) is not less than the lower limit, the cured film obtained by curing the polyisocyanate composition alone has low hardness and more excellent flexibility. In addition, an adhesive sheet having more excellent adhesion and curability can be obtained.
The content of the polyol (B1) can be calculated, for example, from the amount of the diisocyanate and the polyol (B1) blended in the production of the isocyanate composition 1.
< Method for producing polyisocyanate composition 1 >
The polyisocyanate is obtained by reacting the diisocyanate, the polyol (A1) and the polyol (B1). Hereinafter, the polyol (A1) and the polyol (B1) may be simply referred to as "polyols" together.
The polyol (A1) and the polyol (B1) may be used individually or in the form of a mixture. When used as a mixture, the polyols may be mixed before reacting with the diisocyanate, or may be mixed after reacting each polyol with the diisocyanate alone to form the polyisocyanate.
Specifically, examples of the method for producing the polyisocyanate composition 1 include a method in which the diisocyanate, the polyol (A1) and the polyol (B1) are simultaneously reacted to obtain the polyisocyanate composition 1, a method in which the product obtained by reacting the diisocyanate with the polyol (A1) and the product obtained by reacting the diisocyanate with the polyol (B1) are mixed to obtain the polyisocyanate composition 1, and a method in which the diisocyanate is reacted with the polyol (A1) or the polyol (B1) and then the remaining polyol is further reacted to obtain the polyisocyanate composition 1. Alternatively, a method may be employed in which a part of the polyol (A1) is added first to obtain the polyisocyanate composition 1, and then the remaining polyol (A1) is added to react with the obtained polyisocyanate composition 1 to obtain the polyisocyanate composition 1.
Regarding the blending amount of the polyol (A1) and the polyol (B1), it is preferable to compound the polyol (A1) so that the mass ratio of the polyol (A1) to the polyol (B1) falls within the above range.
In the reaction, the molar ratio of isocyanate groups of the diisocyanate to hydroxyl groups of the polyol (A1) and the polyol (B1) (molar ratio of isocyanate groups/hydroxyl groups) is 2 or more and 30 or less, preferably 2.6 or more and 30 or less, more preferably 3 or more and 25 or less, still more preferably 3.5 or more and 24 or less, particularly preferably 5 or more and 23 or less, and most preferably 5 or more and 20 or less.
The reaction of the polyol with the diisocyanate proceeds as follows. The reaction temperature is usually not less than room temperature (about 23 ℃) and not more than 200 ℃, preferably not less than 60 ℃ and not more than 120 ℃. When the reaction temperature is not less than the above-mentioned lower limit, the reaction time is further shortened, and when it is not more than the above-mentioned upper limit, the increase in the viscosity of the polyisocyanate due to the undesired side reaction can be further avoided, and the coloring of the polyisocyanate to be produced can be further avoided.
The reaction may be carried out in the absence of a solvent, or may be carried out using any solvent which is inactive with respect to isocyanate groups. In addition, a known catalyst may be used if necessary to promote the reaction between the isocyanate group and the hydroxyl group.
Physical Properties of polyisocyanate composition 1
The isocyanate group content (NCO group content) of the polyisocyanate composition 1 of the present embodiment is preferably 1% by mass or more and 10% by mass or less, more preferably 1.5% by mass or more and 9.8% by mass or less, still more preferably 2.0% by mass or more and 9.6% by mass or less, still more preferably 2.5% by mass or more and 9.5% by mass or less, still more preferably 2.75% by mass or more and 9.5% by mass or less, particularly preferably 3.0% by mass or more and 9.5% by mass or less, and most preferably 3.15% by mass or more and 9.5% by mass or less, based on the total mass of the polyisocyanate composition 1 in a state where the solvent and the diisocyanate are substantially absent.
The NCO group content can be determined, for example, by reacting the isocyanate groups of the polyisocyanate composition 1 with an excessive amount of amine (dibutylamine or the like), and back-titrating the remaining amine with an acid such as hydrochloric acid.
The average isocyanate functional group number of the polyisocyanate composition 1 of the present embodiment is preferably 2 or more and 6 or less, preferably 2 or more and 5.8 or less, more preferably 2.5 or more and 5.5 or less, from the viewpoint of improving the curability and cohesive force of the adhesive composition.
The average isocyanate functional group number of the polyisocyanate composition 1 of the present embodiment can be measured by the method described in examples described later.
Cured film
The cured film of the present embodiment is obtained by curing the polyisocyanate composition 1.
The cured film of the present embodiment has low hardness and good flexibility.
The cured film of the present embodiment can be produced, for example, by diluting or dissolving the polyisocyanate composition 1 with a solvent as needed, applying the resultant film to an adherend using a coater or the like, and drying the resultant film as needed, and curing the resultant film with heat.
When the cured film of the present embodiment is a cured film having a film thickness of 40 μm, which is formed by a reaction between moisture in the air and the polyisocyanate composition 1 after the polyisocyanate composition 1 is applied to glass, stored for 168 hours in a 23 ℃ and 65% humidity environment, and then heated for 24 hours at 50 ℃, the cured film has a Ke Nixi hardness of 60 times or less, preferably 57 times or less, more preferably 55 times or less, and even more preferably 54 times or less in a 23 ℃ environment. When Ke Nixi has a hardness of not more than the upper limit, the hardness is low and the flexibility is further excellent.
Coating film
The polyisocyanate composition 1 may be used as a curing agent component of a coating composition. That is, the coating film of the present embodiment can be formed by curing a coating composition containing the polyisocyanate composition 1 and a polyol.
In the case where the coating film of the present embodiment is a coating film having a film thickness of 40 μm after curing a coating composition containing the polyisocyanate composition 1 and an acrylic polyol having a glass transition temperature of 29.1 ℃ and a hydroxyl value of 139mgKOH/g relative to the resin solid content and a weight average molecular weight of 2.56×10 4 at 90 ℃ for 30 minutes and storing the coating film in a 23 ℃ and 65% humidity environment for 168 hours, in a tensile test in which a test piece having a width of 10mm and a length of 100mm is set in a tensile tester at a clamp distance of 20mm and measured at a speed of 20 mm/min, the elongation of the coating film is 50% or more and the stress at an elongation of 140% is 28MPa or less. The elongation is preferably 100% or more, more preferably 130% or more, still more preferably 140% or more, and particularly preferably 150% or more. On the other hand, the upper limit of the elongation may be set to 300%, for example.
The stress at 140% elongation is preferably 27MPa or less, more preferably 25MPa or less, and still more preferably 20MPa or less. On the other hand, the lower limit of the stress at 140% elongation may be, for example, 1MPa.
The flexibility of the coating film is further improved by setting the elongation to the lower limit or more and the stress at the elongation of 140% or less to the upper limit or less.
Adhesive composition
The adhesive composition of the present embodiment comprises the polyisocyanate composition 1 and a crosslinkable functional group-containing polymer having a glass transition temperature of 0 ℃ or less.
The adhesive composition of the present embodiment can form an adhesive layer having higher flexibility than conventional adhesive layers by including the polyisocyanate composition 1, and can provide an adhesive sheet excellent in adhesion, cohesion, curability, and transparency.
Next, details of each component contained in the adhesive composition of the present embodiment will be described below.
< Crosslinkable functional group-containing Polymer >
The glass transition temperature of the crosslinkable functional group-containing polymer is 0 ℃ or less, preferably-70 ℃ or more and 0 ℃ or less, more preferably-70 ℃ or more and-5 ℃ or less, still more preferably-70 ℃ or more and-10 ℃ or less, particularly preferably-70 ℃ or more and-15 ℃ or less. When the glass transition temperature Tg of the crosslinkable functional group-containing polymer is in the above range, the adhesive force and cohesive force of the cured product of the adhesive composition tend to be more excellent. For the glass transition temperature of the crosslinkable functional group-containing polymer, for example, an organic solvent and moisture in a solution in which the crosslinkable functional group-containing polymer is dissolved or dispersed are evaporated under reduced pressure, and then vacuum drying is performed, and the obtained material is measured by a Differential Scanning Calorimeter (DSC) measuring apparatus at a temperature rise rate of 5 ℃.
The weight average molecular weight Mw of the crosslinkable functional group-containing polymer is preferably 3.0x10 5 or more and 2.5x10 6 or less, more preferably 4.0x10 5 or more and 2.3x10 6 or less, still more preferably 4.5x10 5 or more and 2.0x10 6, particularly preferably 4.5x10 5 or more and 1.8x10 6 or less. When the weight average molecular weight of the crosslinkable functional group-containing polymer is in the above range, the cured product of the adhesive composition tends to be more excellent in adhesive force, cohesive force and durability. The weight average molecular weight Mw of the polyol can be measured, for example, by the method described in examples described below.
The crosslinkable functional group-containing polymer may be a polymer containing a crosslinkable functional group capable of reacting with an isocyanate group of the polyisocyanate composition 1. Examples of the crosslinkable functional group include a hydroxyl group, a thiol group, an amino group, a carboxyl group, and an epoxy group, and among them, a hydroxyl group is preferable. That is, a polyol is preferable as the crosslinkable functional group-containing polymer.
Examples of the crosslinkable functional group-containing polymer include aliphatic hydrocarbon polyols, polyether polyols, polyester polyols, epoxy resins, fluorine-containing polyols, acrylic polymers, and urethane polymers.
Among them, an acrylic polymer is preferable as the crosslinkable functional group-containing polymer.
[ Aliphatic hydrocarbon polyol ]
Examples of the aliphatic hydrocarbon polyol include terminal-hydroxylated polybutadiene and its hydride.
[ Polyether polyol ]
Examples of the polyether polyol include polyether polyols obtained by any of the following methods (1) to (3). (1) Polyether polyol or polytetramethylene ether glycol obtained by adding an alkylene oxide alone or a mixture thereof to a polyol alone or a mixture thereof. (2) Polyether polyol obtained by reacting a polyfunctional compound with an alkylene oxide. (3) A so-called polymer polyol obtained by polymerizing acrylamide or the like with the polyether polyol obtained in (1) or (2) as a medium.
Examples of the polyhydric alcohol include glycerin and propylene glycol.
Examples of the alkylene oxide include ethylene oxide and propylene oxide.
Examples of the polyfunctional compound include ethylenediamine and ethanolamine.
[ Polyester polyol ]
Examples of the polyester polyol include any of the following (1) and (2). (1) Polyester polyol resins obtained by condensation reaction of a dibasic acid alone or a mixture of 2 or more thereof with a polyol alone or a mixture of 2 or more thereof. (2) And a polycaprolactone polyol obtained by ring-opening polymerization of epsilon-caprolactone with a polyol.
Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1, 4-cyclohexanedicarboxylic acid.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylol propane, glycerol, pentaerythritol, 2-hydroxymethylpropane, and ethoxylated trimethylol propane.
[ Epoxy resin ]
Examples of the epoxy resin include novolac-type epoxy resins, beta-methyl epichlorohydrin-type epoxy resins, cyclic ethylene oxide (epoxy) type epoxy resins, glycidyl ether-type epoxy resins, glycol ether-type epoxy resins, epoxy-type aliphatic unsaturated compounds, epoxidized fatty acid esters, ester-type polycarboxylic acids, aminoglycidyl-type epoxy resins, halogenated epoxy resins, resorcinol-type epoxy resins, and epoxy resins obtained by modifying these epoxy resins with amino compounds, polyamide compounds, and the like.
[ Fluorine-containing polyol ]
Examples of the fluorine-containing polyol include copolymers of fluoroolefins, cyclohexyl vinyl ethers, hydroxyalkyl vinyl ethers, vinyl monocarboxylic acid esters and the like disclosed in reference 1 (Japanese patent application laid-open No. 57-34107) and reference 2 (Japanese patent application laid-open No. 61-275311).
[ Acrylic Polymer ]
The acrylic polymer contains 1 or more polymerizable (meth) acrylic monomer units having a crosslinkable functional group. The crosslinkable functional group preferably contains a hydroxyl group, a carboxyl group, or an epoxy group, and more preferably contains a hydroxyl group.
The acrylic polymer may contain 1 kind of crosslinkable functional group alone or 2 or more kinds of crosslinkable functional groups in combination. That is, the acrylic polymer may be obtained by polymerizing 1 kind of polymerizable (meth) acrylic monomer having a crosslinkable functional group alone, or may be obtained by copolymerizing 2 or more kinds of polymerizable (meth) acrylic monomers having different kinds of crosslinkable functional groups.
The acrylic polymer may contain not only a polymerizable (meth) acrylic monomer unit having a crosslinkable functional group but also 1 or more polymerizable acrylic monomer units having no crosslinkable functional group.
That is, the acrylic polymer can be obtained by polymerizing 1 or more polymerizable (meth) acrylic monomers having a crosslinkable functional group, or can be obtained by copolymerizing 1 or more polymerizable (meth) acrylic monomers having a crosslinkable functional group with 1 or more polymerizable (meth) acrylic monomers having no crosslinkable functional group.
Examples of the polymerizable (meth) acrylic monomer having a crosslinkable functional group include monomers represented by the following (i) to (v). These may be used alone or in combination of 1 or more than 2. (i) Acrylic esters having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, and 6-hydroxyhexyl acrylate. (ii) Methacrylates having a hydroxyl group such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate and 6-hydroxyhexyl methacrylate. (iii) (meth) acrylic esters having a polyhydric hydroxyl group, such as acrylic monoester, methacrylic monoester, and acrylic monoester of trimethylolpropane and methacrylic monoester of glycerin. (iv) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, and the like. (v) Polymerizable monomers having an epoxy group such as glycidyl methacrylate, 1, 2-epoxy-4-vinylcyclohexane, allyl glycidyl ether, and 4-hydroxybutyl acrylate glycidyl ether.
Examples of the polymerizable (meth) acrylic monomer having no crosslinkable functional group include monomers represented by the following (i) to (iii). These may be used alone or in combination of 1 or more than 2. (i) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, nonadecyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic esters such as cyclohexyl (meth) acrylate. (ii) Unsaturated amides such as (meth) acrylamide, N-methylolacrylamide, diacetone acrylamide and dimethylaminopropyl acrylamide. (iii) Styrene, vinyl toluene, vinyl acetate, (meth) acrylonitrile, N-vinyl pyrrolidone, N-vinyl caprolactam, acryloylmorpholine, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate.
Further, as another monomer copolymerizable with the polymerizable (meth) acrylic monomer having a crosslinkable functional group, polymerizable ultraviolet-stable monomers disclosed in Japanese patent application laid-open No. 1-261409 (reference 3), japanese patent application laid-open No. 3-006273 (reference 4) and the like can be used.
As the polymerizable ultraviolet stable monomer, specifically, examples thereof include 4- (meth) acryloyloxy-2, 6-tetramethylpiperidine, 4- (meth) acryloylamino-2, 6-tetramethylpiperidine 1-crotonyl-4-crotonyloxy-2, 6-tetramethylpiperidine, 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, and the like.
Among them, the acrylic polymer preferably contains 1 or more acrylic acid ester units having an alkyl group having 1 to 20 carbon atoms at the ester group terminal.
The acrylate unit having an alkyl group having 1 to 20 carbon atoms at the terminal of the ester group may or may not contain a crosslinkable functional group.
The number of carbon atoms of the alkyl group of the acrylate unit having a crosslinkable functional group is 1 to 20, preferably 1 to 18, more preferably 2 to 18.
On the other hand, the carbon number of the alkyl group of the acrylate unit containing no crosslinkable functional group is 1 to 20, preferably 1 to 18, more preferably 2 to 18, still more preferably 4 to 18.
For example, the above monomer component is subjected to solution polymerization in the presence of a known radical polymerization initiator such as a peroxide or azo compound, and diluted with an organic solvent or the like as necessary, whereby an acrylic polymer can be obtained.
In the case of obtaining an acrylic polymer of an aqueous matrix, the acrylic polymer can be produced by a known method such as a method of solution-polymerizing an olefinically unsaturated compound and converting the olefinically unsaturated compound to an aqueous layer, emulsion-polymerizing, and the like. In this case, the acid moiety of the carboxylic acid-containing monomer such as acrylic acid or methacrylic acid or the sulfonic acid-containing monomer is neutralized with amine or ammonia, whereby water solubility or water dispersibility can be imparted.
[ Isocyanate group/hydroxyl group ]
The molar ratio of isocyanate groups to hydroxyl groups of the polyol (molar ratio of isocyanate groups/hydroxyl groups) of the polyisocyanate composition 1 contained in the resin composition of the present embodiment can be determined according to the physical properties required for the resin film, and is usually 0.01 to 22.5.
< Other ingredients >
The resin composition of the present embodiment may further contain other additives.
Examples of the other additives include a curing agent, a curing catalyst, a solvent, pigments (extender pigment, coloring pigment, metallic pigment, etc.), a tackifying resin, a photopolymerization initiator, an ultraviolet absorber, a light stabilizer, a radical stabilizer, a yellowing inhibitor for inhibiting coloring in the sintering step, a coating surface regulator, a flow regulator, a pigment dispersant, an antifoaming agent, a thickener, a film forming aid, and the like, which are other than the polyisocyanate composition 1 and which are reactive with the polyol.
Examples of the curing agent include melamine resins, urea resins, epoxy group-containing compounds or resins, carboxyl group-containing compounds or resins, acid anhydrides, alkoxysilane-containing compounds or resins, and hydrazide compounds.
The curing catalyst may be a basic compound or a lewis acidic compound.
Examples of the basic compound include metal hydroxides, metal alkoxides, metal carboxylates, metal acetylacetonates, hydroxides of onium salts, onium carboxylates, halides of onium salts, metal salts of active methylene compounds, onium salts of active methylene compounds, aminosilanes, amines, phosphines, and the like. As the aforementioned onium salt, ammonium salt, phosphonium salt or sulfonium salt is preferable.
Examples of the lewis acidic compound include an organotin compound, an organozinc compound, an organotitanium compound, and an organozirconium compound.
Examples of the solvent include 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether (DPDM), propylene glycol dimethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethanol, methanol, isopropanol, 1-propanol, isobutanol, 1-butanol, t-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, isopentane, hexane, isohexane, cyclohexane, solvent naphtha, and mineral spirits. These solvents may be used singly or in combination of 2 or more.
The pigment (extender pigment, coloring pigment, metallic pigment, etc.), ultraviolet absorber, light stabilizer, radical stabilizer, yellowing inhibitor for inhibiting coloring in the sintering step, coating surface regulator, flow regulator, pigment dispersant, defoamer, thickener, and film forming aid may be appropriately selected and used.
< Method for producing adhesive composition >
The adhesive composition can be produced by a known method. For example, a melt kneading method using a general mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, or a multi-screw extruder, or a method in which each component is dissolved or dispersed and mixed, and then applied to a base film by a coater or the like, and then the solvent is removed by heating, are used.
In order to achieve the effects of weight reduction, softening, and improvement of adhesion, the adhesive composition of the present embodiment may be foamed. As the foaming method, there are a chemical method, a physical method, a method using thermally expandable microspheres, and the like. The foam may be distributed in the material by adding a chemical foaming agent such as an inorganic foaming agent or an organic foaming agent, a physical foaming agent, or the like, or by adding thermally expandable microspheres, or the like, respectively.
In addition, by adding a hollow filler (expanded ball), weight reduction, softness, and improvement of adhesion can be achieved.
The adhesive composition of the present embodiment may contain a tackifying resin to adjust the adhesive force and cohesive force. Examples of the tackifying resin include rosin-based tackifying resins, terpene-based tackifying resins, petroleum-based tackifying resins, and styrene-based tackifying resins. These tackifying resins may be used alone or in combination of 2 or more. The softening point of the tackifying resin is preferably 90 ℃ or more and 160 ℃ or less.
Adhesive sheet
The pressure-sensitive adhesive sheet of the present embodiment includes a base material and a pressure-sensitive adhesive layer provided on the base material.
The adhesive layer contains a cured product of the adhesive composition.
In the pressure-sensitive adhesive sheet of the present embodiment, the pressure-sensitive adhesive layer is excellent in adhesiveness, curability, and transparency.
Examples of the substrate include, but are not particularly limited to, papers such as high-quality papers, coated papers, cast papers, thermal papers, and inkjet papers, cloths such as woven fabrics and nonwoven fabrics, resin films such as polyvinyl chloride, synthetic papers, polyethylene terephthalate (PET), polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, polystyrene, polycarbonate, nylon, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and polyimide, porous resin films such as porous polypropylene films, vapor deposition films obtained by vapor deposition of metals such as aluminum on PET, polyolefin, and the like, and metal foils. The substrate may be a substrate having a surface subjected to a peeling treatment.
In the pressure-sensitive adhesive sheet of the present embodiment, the thickness of the pressure-sensitive adhesive layer can be appropriately determined depending on the application, and is preferably 1 μm or more and 1000 μm or less, more preferably 5 μm or more and 900 μm or less, still more preferably 7 μm or more and 800 μm or less, and particularly preferably 9 μm or more and 700 μm or less.
The adhesive sheet of the present embodiment can be produced, for example, by applying the adhesive composition to a substrate, drying it as necessary, and thereafter curing it.
Examples of the method for applying the adhesive composition to the substrate include a method of applying the adhesive composition using an applicator, a roll coater, a doctor blade coater, a gravure coater, and the like. In the case of drying after the coating, for example, a heat drying method in which the obtained laminate is put into a dryer or the like and dried at a temperature of, for example, 50 ℃ or more and 150 ℃ or less for 1 minute or more and 30 minutes or less is exemplified. Alternatively, examples of the other drying method include natural drying, hot air drying, and infrared drying.
The heating temperature at the time of curing may be 70 ℃ to 150 ℃, 75 ℃ to 145 ℃, or 80 ℃ to 140 ℃.
The pressure-sensitive adhesive sheet of the present embodiment is obtained by wrapping a pressure-sensitive adhesive sheet having a 50 μm thick pressure-sensitive adhesive layer, which is obtained by applying the pressure-sensitive adhesive composition to a peel-treated polyethylene terephthalate film having a thickness of 38 μm, and drying the film at 130 ℃ for 3 minutes after drying the film at 120 ℃ for 3 minutes, wherein the pressure-sensitive adhesive sheet is prepared by immersing the pressure-sensitive adhesive sheet in ethyl acetate at 23 ℃ for 1 week after storage for 7 days in a 50% RH environment at 23 ℃ and drying the film at 120 ℃ for 2 hours, preferably at least 25% by mass and at most 99% by mass, more preferably at least 30% by mass and at most 99% by mass, particularly preferably at least 35% by mass and at most 99% by mass, most preferably at least 40% by mass and at most 99% by mass. By setting the gel fraction to the above lower limit or more, the curability is further improved.
The gel fraction referred to herein is a mass percentage of the adhesive sheet obtained by immersing the adhesive sheet in ethyl acetate and drying the adhesive sheet with respect to the mass of the adhesive sheet before immersing the adhesive sheet in ethyl acetate.
The pressure-sensitive adhesive sheet of the present embodiment is produced by subjecting a pressure-sensitive adhesive sheet having a thickness of 50 μm, which is preferably a 180-degree peel adhesion of 0.05N/20mm or more and 55N/20mm or less, more preferably 0.07N/20mm or more and 45N/20mm or less, still more preferably 0.1N/20mm or more and 38N/20mm or less, particularly preferably 0.12N/20mm or more and 36N/20mm or less, most preferably 0.15N/20mm or more and 33N/20mm or less, to back and forth pressure-sensitive adhesive treatment with a 2kg roller after storage for 7 days in a 23 DEG, curing at 23 ℃ for 30 minutes, and then applying the pressure-sensitive adhesive composition to a polyethylene terephthalate film having a thickness of 25 μm, which is preferably dried at 130 ℃ for 3 minutes, and curing. The 180-degree peel adhesion is set to the lower limit or more, whereby the adhesion is further excellent.
In the pressure-sensitive adhesive sheet of the present embodiment, the pressure-sensitive adhesive composition is applied to a release-treated polyethylene terephthalate film having a thickness of 38 μm, and dried at 130 ℃ for 3 minutes, and then the pressure-sensitive adhesive layer having a thickness of 50 μm formed by curing is released from the release-treated polyethylene terephthalate film and then bonded to a glass having a haze value of 0.1%, and the haze value of the pressure-sensitive adhesive sheet obtained by the above method is preferably 0.01% or more and 2% or less, more preferably 0.01% or more and 1.8% or less, still more preferably 0.01% or more and 1.5% or less, particularly preferably 0.01% or more and 1.0% or less, and most preferably 0.01% or more and 0.8% or less, as measured by a haze meter. By setting the haze value to the above upper limit value or less, the transparency is further excellent.
Polyisocyanate composition 2
The polyisocyanate composition 2 of the present embodiment is derived from diisocyanate, polycaprolactone polyol (A2), and polyether polyol (B2). That is, the polyisocyanate composition 2 of the present embodiment is a reaction product of a diisocyanate and a polycaprolactone polyol (A2) and a polyether polyol (B2), and contains a polyisocyanate modified with the polycaprolactone polyol (A2) and the polyether polyol (B2). The diisocyanate is at least 1 selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.
The polyisocyanate composition 2 of the present embodiment contains 20 parts by mass or more of polypropylene glycol per 100 parts by mass of the polyether polyol (B2).
The polyisocyanate composition 2 of the present embodiment, which uses 2 different polyols and includes polypropylene glycol as the polyether polyol (B2) as described above, exhibits higher flexibility than before, specifically, has good compatibility with a main agent in a low-temperature environment of about-10 ℃ and can give a coating film excellent in flexibility at a low temperature of about-10 ℃ and at normal temperature of about 23 ℃.
Next, the details of the components of the polyisocyanate composition 2 according to the present embodiment will be described below.
< Polyisocyanate >
The polyisocyanate composition 2 of the present embodiment may be a polyisocyanate having a structural unit derived from each of the diisocyanate, the polycaprolactone polyol (A2), and the polyether polyol (B2) in one molecule, or may be a mixture of polyisocyanates having at least 1 structural unit derived from the group consisting of the diisocyanate, the polycaprolactone polyol (A2), and the polyether polyol (B2) in one molecule.
The polyisocyanate may have at least 1 or more structures selected from the group consisting of an allophanate structure, a uretdione structure, an iminooxadiazinedione structure, an isocyanurate structure, a urea structure, a urethane structure, and a biuret structure. Among them, at least 1 structure selected from the group consisting of a urethane structure, an allophanate structure, a biuret structure, a urea structure, and an isocyanurate group is preferable.
[ Diisocyanate ]
The diisocyanate is at least 1 selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.
The aliphatic diisocyanate is not limited to the following, and examples thereof include 1, 4-diisocyanatobutane, 1, 5-diisocyanatopentane, ethyl (2, 6-diisocyanato) hexanoate, 1, 6-diisocyanatohexane (hereinafter, sometimes abbreviated as "HDI"), 1, 9-diisocyanatononane, 1, 12-diisocyanato dodecane, 2, 4-or 2, 4-trimethyl-1, 6-diisocyanatohexane, and the like. These aliphatic diisocyanates may be used singly or in combination of 2 or more.
Examples of the alicyclic diisocyanate include, but are not limited to, 1, 3-or 1, 4-bis (isocyanatomethyl) cyclohexane (hereinafter, sometimes abbreviated as "hydrogenated XDI"), 1, 3-or 1, 4-diisocyanatocyclohexane, 3, 5-trimethyl 1-isocyanato-3- (isocyanatomethyl) cyclohexane (hereinafter, sometimes abbreviated as "IPDI"), 4-4' -diisocyanato-dicyclohexylmethane (hereinafter, sometimes abbreviated as "hydrogenated MDI"), 2, 5-or 2, 6-diisocyanatomethyl norbornane, and the like. These alicyclic diisocyanates may be used singly or in combination of 2 or more.
These aliphatic diisocyanate and alicyclic diisocyanate may be used alone, the aliphatic diisocyanate and the alicyclic diisocyanate may be used in combination of 2 or more.
Among them, as the diisocyanate, HDI, IPDI, hydrogenated XDI or hydrogenated MDI is preferable, HDI or IPDI is more preferable, and HDI is further preferable.
In the production of the polyisocyanate, an isocyanate monomer as shown below may be used in addition to the diisocyanate.
(1) Aromatic diisocyanates such as diphenylmethane-4, 4' -diisocyanate (MDI), 1, 5-naphthalene diisocyanate, toluene Diisocyanate (TDI), xylylene diisocyanate, and m-tetramethylxylylene diisocyanate (TMXDI).
(2) Triisocyanates such as 4-isocyanatomethyl-1, 8-octamethylenediisocyanate (hereinafter sometimes referred to as "NTI"), 1,3, 6-hexamethylene triisocyanate (hereinafter sometimes referred to as "HTI"), bis (2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter sometimes referred to as "GTI"), and lysine triisocyanate (hereinafter sometimes referred to as "LTI").
< Polycaprolactone polyol (A2) >
The polycaprolactone polyol is not particularly limited, and specifically can be obtained by ring-opening polymerization of epsilon-caprolactone in the presence of a catalyst using a 2-membered or more, preferably 3-membered alcohol as an initiator. The initiator is not particularly limited, and specifically, 2-alcohols such as ethylene glycol, propylene glycol, 1, 3-butanediol, neopentyl glycol, etc., 3-alcohols such as trimethylolpropane, glycerin, etc., may be used. From the viewpoint of obtaining a polyisocyanate having a low viscosity, a polycaprolactone polyol having a branched chain is preferable. Such polycaprolactone polyols can be obtained by using 3-membered or more alcohols as initiators.
The catalyst is not particularly limited, and specifically, organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, and tin compounds such as tin octoate, dibutyltin oxide, dibutyltin laurate, stannous chloride, and stannous bromide can be used.
The ring-opening polymerization of epsilon-caprolactone is not particularly limited, and specifically, the ring-opening polymerization may be carried out by adding 0.1 mass ppm or more and 100 mass ppm or less of a catalyst to epsilon-caprolactone in such a manner that the molar ratio of epsilon-caprolactone to the initiator is set to a desired molecular weight in a nitrogen atmosphere, and reacting at a temperature of 150 ℃ or more and 200 ℃ or less for 4 hours or more and 10 hours or less.
The polyisocyanate is formed with urethane groups by the reaction of the hydroxyl groups of the polycaprolactone polyol (A2) with the isocyanate groups of the diisocyanate.
The average hydroxyl functional group number of the polycaprolactone polyol (A2) is preferably 2.0 or more and 8.0 or less, more preferably 2 or more and 6 or less, further preferably 2 or more and 5 or less, particularly preferably 3. The average hydroxyl functional group number of the polycaprolactone polyol (A2) referred to herein is the number of hydroxyl groups present in 1 molecule of the polycaprolactone polyol (A2).
The number average molecular weight of the polycaprolactone polyol (A2) is preferably 500 or more and 1500 or less, more preferably 600 or more and 1400 or less, still more preferably 700 or more and 1300 or less, and particularly preferably 850 or more and 1250 or less.
The number average molecular weight of the polycaprolactone polyol (A2) is in the above range, and thus the coating film obtained is more excellent in flexibility at low temperature and normal temperature. The number average molecular weight Mn of the polycaprolactone polyol (A2) is, for example, a polystyrene-based number average molecular weight measured by Gel Permeation Chromatography (GPC).
Examples of the commercially available polycaprolactone polyols include "PLACCEL 305" (number average molecular weight 550), "PLACCEL 308" (number average molecular weight 850), "PLACCEL 309" (number average molecular weight 900), "PLACCEL 312" (number average molecular weight 1250), "PLACCEL 205" (number average molecular weight 530), "PLACCEL 210" (number average molecular weight 1000) manufactured by Dairy, and "POLYLITE OD-X-2735" (number average molecular weight 500), "POLYLITE OD-X-2586" (number average molecular weight 850), "POLYLITE OD-X-2588" (number average molecular weight 1250) manufactured by DIC corporation.
< Polyether polyol (B2) >)
The polyether polyol (B2) contains polypropylene glycol (PPG, also referred to as polyoxypropylene polyol).
In the polyisocyanate composition 2 of the present embodiment, the PPG content is 20 parts by mass or more, preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 55 parts by mass or more, particularly preferably 60 parts by mass, and most preferably 100 parts by mass with respect to 100 parts by mass of the polyether polyol (B2). By setting the PPG content to the above lower limit or more, compatibility with the main agent in a low-temperature environment can be improved.
The polypropylene glycol is not particularly limited, and specific examples thereof include polyoxypropylene glycol or triol, so-called Pluronic (registered trademark) polyoxypropylene glycol or triol in which ethylene oxide is added and polymerized to the terminal end of polyoxypropylene glycol or triol, polyoxypropylene polyoxyethylene polymer glycol or triol, and the like. Among them, the aforementioned Pluronic (registered trademark) polyoxypropylene diol or triol is preferable from the viewpoint of excellent reactivity with diisocyanate.
As a method for producing polypropylene glycol, there is a method in which propylene oxide, ethylene oxide used if necessary, or the like is added to an initiator and a catalyst singly or in a mixture. The initiator is not particularly limited, and specifically includes polyols, polyphenols, polyamines, alkanolamines, or mixtures of these, and more specifically includes 2-alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 6-hexanediol, bisphenol a, 3-alcohols such as glycerin and trimethylolpropane, diamines such as ethylenediamine, and mixtures of these. The catalyst is not particularly limited, and specifically includes hydroxides such as lithium, sodium and potassium, strong basic catalysts such as alkoxides and alkylamines, and complex metal complexes such as metalloporphyrins, complex metal cyanide complexes, complexes of a metal with a chelating agent of a ligand having 3 or more teeth, and zinc hexacyanocobaltate complexes. Further, a method of dehydrating and condensing a polyol to obtain polypropylene glycol is exemplified.
As the commercially available polypropylene glycol, trade names "EXCENOL 510" (EO-tipped polyoxypropylene glycol, number average molecular weight 4000), "EXCENOL 840" (EO-tipped polyoxypropylene triol, number average molecular weight 6500), "EXCENOL" (EO-tipped polyoxypropylene glycol, number average molecular weight 1000), "EXCENOL 2020" (EO-tipped polyoxypropylene glycol, number average molecular weight 2000) and the like manufactured by Asahi Kabushiki Kaisha are exemplified.
The polyether polyol (B2) may contain other polyether polyols in addition to polypropylene glycol.
Examples of the other polyether polyols include, but are not particularly limited to, polyether polyols obtained by adding an alkylene oxide alone or a mixture thereof to a polyol alone or a mixture thereof using an alkali metal hydroxide or a strong alkali catalyst, polyether polyols obtained by reacting an alkylene oxide with a polyamine compound, and so-called polymer polyols obtained by polymerizing acrylamide or the like with the polyether as a medium.
Examples of the alkali metal include lithium, sodium, and potassium. Examples of the strong basic catalyst include alkoxides and alkylamines.
The polyhydric alcohol is not particularly limited, and examples thereof include at least 1 polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylol propane, and glycerin.
Examples of the alkylene oxide include ethylene oxide, butylene oxide, cyclohexane oxide, and styrene oxide.
Examples of the polyamine compound include ethylenediamine.
Among them, polytetramethylene ether glycol (PTMG, also referred to as polyoxytetramethylene polyol) is preferable as the other polyether polyol.
Polytetramethylene ether glycol can be produced by cationic polymerization of tetrahydrofuran using a catalyst, and the like. The catalyst to be used is not particularly limited, and acetic anhydride-perchloric acid, fluorosulfonic acid, fuming sulfuric acid, or the like can be specifically used. For example, the production of polyoxytetramethylene glycol is not particularly limited, and specifically, it is generally carried out under conditions in which fluorosulfonic acid is added to tetrahydrofuran as a raw material in an amount of about 1 mass% to 30 mass% and the reaction is carried out at a temperature of 5 ℃ to 65 ℃ for several minutes to several tens of hours. In addition, the polypropylene glycol can be produced by using a polyol or the like as an initiator and performing addition of butylene oxide using a strong basic catalyst or the like, as in the above-described method for producing polypropylene glycol. In addition, the molecular weight of the polytetramethylene ether glycol produced can be adjusted by changing the polymerization temperature, polymerization time, catalyst amount, etc.
Examples of the commercially available polytetramethylene ether glycol include "PTMG1000" (number average molecular weight 1000), "PTMG2000" (number average molecular weight 2000), "PTMG3000" (number average molecular weight 2900), "PTMG4000" (number average molecular weight 4000) manufactured by Mitsubishi chemical corporation.
The mass ratio of polytetramethylene ether glycol to polypropylene glycol (mass ratio of PTMG/PPG) in the polyether polyol (B2) is preferably 0/100 or more and 80/20 or less, more preferably 0/100 or more and 60/40 or less, still more preferably 0/100 or more and 50/50 or less, particularly preferably 0/100 or more and 45/55 or less. By making the mass ratio of PTMG/PPG within the above range, compatibility with the main agent in a low-temperature environment can be made better.
The number average molecular weight of the polyether polyol (B2) is preferably 1000 to 7000, more preferably 2000 to 7000, still more preferably 3000 to 6700, particularly preferably 4000 to 6500.
When the number average molecular weight of the polyether polyol (B2) is in the above range, the resulting coating film is more excellent in flexibility at low temperature and normal temperature. The number average molecular weight Mn of the polyether polyol (B2) is, for example, the number average molecular weight based on polystyrene measured by GPC. When 2 or more polyether polyols (B2) are mixed and used, the number average molecular weight of the mixture is calculated.
In the polyisocyanate composition 2 of the present embodiment, the mass ratio of the polycaprolactone polyol (A2) to the polyether polyol (B2) ((mass ratio of A2)/(B2)) is preferably 10/90 or more and 90/10 or less, more preferably 15/85 or more and 85/15 or less, still more preferably 18/82 or more and 83/17 or less.
By setting the mass ratio of (A2)/(B2) to the above lower limit or more, the compatibility with the main agent in a low-temperature environment can be improved. On the other hand, when the upper limit value is not more than the above, a coating film having more excellent flexibility at low temperature and normal temperature can be obtained.
(A2) The mass ratio/(B2) can be calculated, for example, from the compounding amount of each polyol.
< Method for producing polyisocyanate composition 2 >
The polyisocyanate is obtained by reacting the above-mentioned diisocyanate, polycaprolactone polyol (A2), and polyether polyol (B2). The polycaprolactone polyol (A2) and the polyether polyol (B2) are sometimes referred to as a polyol in the following.
The polycaprolactone polyols (A2) and the polyether polyols (B2) can be used individually or in the form of mixtures. When used as a mixture, the polyols may be mixed before reacting with the diisocyanate, or may be mixed after reacting each polyol with the diisocyanate alone to form the polyisocyanate.
Specifically, examples of the method for producing the polyisocyanate composition 2 include a method in which a diisocyanate, a polycaprolactone polyol (A2), and a polyether polyol (B2) are simultaneously reacted to obtain the polyisocyanate composition 2, a method in which a product obtained by reacting a diisocyanate with a polycaprolactone polyol (A2) is mixed with a product obtained by reacting a diisocyanate with a polyether polyol (B2) to obtain the polyisocyanate composition 2, and a method in which a diisocyanate is reacted with a polycaprolactone polyol (A2) or a polyether polyol (B2) and then the remaining polyol is further reacted to obtain the polyisocyanate composition 2.
Regarding the compounding amount of the polycaprolactone polyol (A2) and the polyether polyol (B2), it is preferable to compound the polycaprolactone polyol (A2) so that the mass ratio of the polycaprolactone polyol to the polyether polyol (B2) is within the above-described range.
The reaction of the polyol with the diisocyanate proceeds as follows. The reaction temperature is usually not less than room temperature (about 23 ℃) and not more than 200 ℃, preferably not less than 80 ℃ and not more than 120 ℃. When the reaction temperature is not less than the above-mentioned lower limit, the reaction time is further shortened, and when it is not more than the above-mentioned upper limit, the increase in the viscosity of the polyisocyanate due to the undesired side reaction can be further avoided, and the coloring of the polyisocyanate to be produced can be further avoided.
The reaction may be carried out in the absence of a solvent, or may be carried out using any solvent which is inactive with respect to isocyanate groups. In addition, a known catalyst may be used if necessary to promote the reaction between the isocyanate group and the hydroxyl group.
In the reaction, the molar ratio of isocyanate groups of the diisocyanate to hydroxyl groups of the polycaprolactone polyol (A2) and the polyether polyol (B2) (molar ratio of hydroxyl groups/isocyanate groups) is preferably 2 or more and 10 or less, more preferably 3 or more and 9 or less, still more preferably 4 or more and 8 or less. By setting the molar ratio of hydroxyl groups to isocyanate groups to the above lower limit or more, it is possible to further avoid an increase in the viscosity of the polyisocyanate due to the successive addition reaction between the diisocyanate and the polyol. On the other hand, when the upper limit value is equal to or less than the above, the productivity is improved.
At the end of the reaction, unreacted diisocyanate in the reaction mixture may be recovered by a known method such as a thin film distillation apparatus, solvent extraction, or the like. The smaller the residual amount of unreacted diisocyanate, the more the odor, toxicity, irritation, etc. due to diisocyanate can be avoided further at the time of heat curing.
Physical Properties of polyisocyanate composition 2
The isocyanate group content (NCO group content) of the polyisocyanate composition 2 of the present embodiment is preferably 3% by mass or more and 8% by mass or less, more preferably 3.1% by mass or more and 7.5% by mass or less, and still more preferably 3.3% by mass or more and 7.3% by mass or less, relative to the total mass of the polyisocyanate composition 2 in a state where the solvent and the diisocyanate are substantially absent.
The NCO group content can be determined, for example, by reacting the isocyanate groups of the polyisocyanate composition 2 with an excessive amount of amine (dibutylamine or the like), and back-titrating the remaining amine with an acid such as hydrochloric acid.
Resin composition
The resin composition of the present embodiment contains the polyisocyanate composition 2 described above as a curing agent component and a polyol as a main component.
The resin composition of the present embodiment can provide a coating film having excellent flexibility at a low temperature of about-10 ℃ and at a normal temperature of about 23 ℃ by containing the polyisocyanate composition 2 as a curing agent component.
The resin composition of the present embodiment can be used for, for example, architectural coatings, automotive repair coatings, plastic coatings, adhesives, binders, building materials, household water-based coatings, other coating agents, sealants, inks, injection molding materials, elastomers, foams, plastic materials, fiber treatment agents, and the like.
Among these, the resin composition of the present embodiment is preferably used as a binder composition, particularly from the viewpoint of good flexibility at low temperature and normal temperature when a coating film is formed.
Next, details of each constituent component contained in the resin composition according to the present embodiment will be described below.
< Polyol >
Specific examples of the polyol include aliphatic hydrocarbon polyols, polyether polyols, polyester polyols, epoxy resins, fluorine-containing polyols, and acrylic polyols.
Among them, an acrylic polyol is preferable as the polyol.
[ Aliphatic hydrocarbon polyol ]
Examples of the aliphatic hydrocarbon polyol include terminal-hydroxylated polybutadiene and its hydride.
[ Polyether polyol ]
Examples of the polyether polyol include polyether polyols obtained by any of the following methods (1) to (3).
(1) Polyether polyol or polytetramethylene ether glycol obtained by adding an alkylene oxide alone or a mixture thereof to a polyol alone or a mixture thereof. (2) Polyether polyol obtained by reacting a polyfunctional compound with an alkylene oxide.
(3) A so-called polymer polyol obtained by polymerizing acrylamide or the like with the polyether polyol obtained in (1) or (2) as a medium.
Examples of the polyhydric alcohol include glycerin and propylene glycol.
Examples of the alkylene oxide include ethylene oxide and propylene oxide.
Examples of the polyfunctional compound include ethylenediamine and ethanolamine.
[ Polyester polyol ]
Examples of the polyester polyol include any of the following (1) and (2).
(1) Polyester polyol resins obtained by condensation reaction of a dibasic acid alone or a mixture of 2 or more thereof with a polyol alone or a mixture of 2 or more thereof.
(2) And a polycaprolactone polyol obtained by ring-opening polymerization of epsilon-caprolactone with a polyol.
Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1, 4-cyclohexanedicarboxylic acid.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylol propane, glycerol, pentaerythritol, 2-hydroxymethylpropane, and ethoxylated trimethylol propane.
[ Epoxy resin ]
Examples of the epoxy resin include novolac-type epoxy resins, beta-methyl epichlorohydrin-type epoxy resins, cyclic ethylene oxide (epoxy) type epoxy resins, glycidyl ether-type epoxy resins, glycol ether-type epoxy resins, epoxy-type aliphatic unsaturated compounds, epoxidized fatty acid esters, ester-type polycarboxylic acids, aminoglycidyl-type epoxy resins, halogenated epoxy resins, resorcinol-type epoxy resins, and epoxy resins obtained by modifying these epoxy resins with amino compounds, polyamide compounds, and the like.
[ Fluorine-containing polyol ]
Examples of the fluorine-containing polyol include copolymers of fluoroolefins, cyclohexyl vinyl ethers, hydroxyalkyl vinyl ethers, vinyl monocarboxylic acid esters and the like disclosed in reference 1 (Japanese patent application laid-open No. 57-34107) and reference 2 (Japanese patent application laid-open No. 61-275311).
[ Acrylic polyol ]
The acrylic polyol can be obtained, for example, by polymerizing a polymerizable monomer having 1 or more active hydrogens in one molecule, or copolymerizing a polymerizable monomer having 1 or more active hydrogens in one molecule with another monomer copolymerizable with the polymerizable monomer, if necessary.
Examples of the polymerizable monomer having 1 or more active hydrogens in one molecule include monomers shown in the following (i) to (iii). These may be used alone or in combination of 1 or more than 2.
(I) Acrylic esters having active hydrogen such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 2-hydroxybutyl acrylate.
(Ii) Methacrylate esters having active hydrogen such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 2-hydroxybutyl methacrylate.
(Iii) (meth) acrylic acid esters having a plurality of active hydrogens, such as acrylic acid monoester, methacrylic acid monoester, and acrylic acid monoester of trimethylolpropane and methacrylic acid monoester of glycerol.
Examples of the other monomer copolymerizable with the polymerizable monomer include monomers represented by the following (i) to (v). These may be used alone or in combination of 1 or more than 2.
(I) Acrylic esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate.
(Ii) Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, glycidyl methacrylate and other methacrylates.
(Iii) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, and the like. (iv) Unsaturated amides such as acrylamide, N-methylolacrylamide and diacetone acrylamide.
(V) Styrene, vinyl toluene, vinyl acetate, acrylonitrile, and the like.
Examples of the polymer include an acrylic polyol obtained by copolymerizing polymerizable ultraviolet-stable monomers disclosed in reference 3 (JP-A-1-261409) and reference 4 (JP-A-3-006273).
As the polymerizable ultraviolet stable monomer, specifically, examples thereof include 4- (meth) acryloyloxy-2, 6-tetramethylpiperidine, 4- (meth) acryloylamino-2, 6-tetramethylpiperidine 1-crotonyl-4-crotonyloxy-2, 6-tetramethylpiperidine, 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, and the like.
For example, the above monomer component is subjected to solution polymerization in the presence of a known radical polymerization initiator such as a peroxide or azo compound, and diluted with an organic solvent or the like as necessary, whereby an acrylic polyol can be obtained.
In the case of the acrylic polyol to obtain the aqueous matrix, the aqueous matrix can be produced by a known method such as a method of solution-polymerizing an olefinically unsaturated compound and converting the olefinically unsaturated compound to an aqueous layer, emulsion polymerization, and the like. In this case, the acid moiety of the carboxylic acid-containing monomer such as acrylic acid or methacrylic acid or the sulfonic acid-containing monomer is neutralized with amine or ammonia, whereby water solubility or water dispersibility can be imparted.
[ Isocyanate group/hydroxyl group ]
The molar ratio of isocyanate groups to hydroxyl groups of the polyol (molar ratio of isocyanate groups/hydroxyl groups) of the polyisocyanate composition 2 contained in the resin composition of the present embodiment can be determined according to the physical properties required for the resin film, and is usually 0.01 to 22.5.
< Other ingredients >
The resin composition of the present embodiment may further contain other additives.
Examples of the other additives include curing agents, curing catalysts, solvents, pigments (extender pigments, coloring pigments, metallic pigments, etc.), photopolymerization initiators, ultraviolet absorbers, light stabilizers, radical stabilizers, yellowing inhibitors for inhibiting coloring in the sintering step, coating surface regulators, flow regulators, pigment dispersants, defoamers, thickeners, film forming aids, and the like, other than the polyisocyanate composition 2, which is reactive with the polyol.
Examples of the curing agent include melamine resins, urea resins, epoxy group-containing compounds or resins, carboxyl group-containing compounds or resins, acid anhydrides, alkoxysilane-containing compounds or resins, and hydrazide compounds.
The curing catalyst may be a basic compound or a lewis acidic compound.
Examples of the basic compound include metal hydroxides, metal alkoxides, metal carboxylates, metal acetylacetonates, hydroxides of onium salts, onium carboxylates, halides of onium salts, metal salts of active methylene compounds, onium salts of active methylene compounds, aminosilanes, amines, phosphines, and the like. As the aforementioned onium salt, ammonium salt, phosphonium salt or sulfonium salt is preferable. Examples of the lewis acidic compound include an organotin compound, an organozinc compound, an organotitanium compound, and an organozirconium compound.
Examples of the solvent include 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether (DPDM), propylene glycol dimethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethanol, methanol, isopropanol, 1-propanol, isobutanol, 1-butanol, t-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, isopentane, hexane, isohexane, cyclohexane, solvent naphtha, and mineral spirits. These solvents may be used singly or in combination of 2 or more.
The pigment (extender pigment, coloring pigment, metallic pigment, etc.), ultraviolet absorber, light stabilizer, radical stabilizer, yellowing inhibitor for inhibiting coloring in the sintering step, coating surface regulator, flow regulator, pigment dispersant, defoamer, thickener, and film forming aid may be appropriately selected and used.
< Method for producing resin composition >
The resin composition of the present embodiment can be produced by a conventionally known method.
When the resin composition of the present embodiment is a binder composition, for example, a melt kneading method using a general mixer such as a Banbury mixer, a single screw extruder, a twin screw extruder, a co-kneader, or a multi-screw extruder, a method in which the components are dissolved or dispersed and mixed, and a method in which the solvent is removed by heating after being applied to a base film by a coater or the like, can be used.
In order to achieve the effects of weight reduction, softening, and adhesion improvement, the resin composition of the present embodiment may be foamed. As the foaming method, there are a chemical method, a physical method, a method using thermally expandable microspheres, and the like. The foam may be distributed in the material by adding a chemical foaming agent such as an inorganic foaming agent or an organic foaming agent, a physical foaming agent, or the like, or by adding thermally expandable microspheres, or the like, respectively.
In addition, by adding a hollow filler (expanded ball), weight reduction, softness, and improvement of adhesion can be achieved.
When the resin composition of the present embodiment is an adhesive composition, a tackifying resin may be added to adjust the adhesive force and cohesive force. Examples of the tackifying resin include rosin-based tackifying resins, terpene-based tackifying resins, petroleum-based tackifying resins, and styrene-based tackifying resins. These tackifying resins may be used alone or in combination of 2 or more. The softening point of the tackifying resin is preferably 90 ℃ or more and 160 ℃ or less.
Examples
The present embodiment will be described in more detail below based on examples and comparative examples, but the present embodiment is not limited to the following examples.
< Test item >
The physical properties of the polyisocyanate compositions produced in examples and comparative examples were measured and evaluated by the methods shown below.
[ Physical Property 1] (isocyanate group content)
First, 2g to 3g (Wg) of a measurement sample are precisely weighed in a flask. Then, 20mL of toluene was added thereto, and the measurement sample was dissolved. Then, 20mL of a toluene solution of 2 equivalents of di-n-butylamine was added and mixed, followed by standing at room temperature for 15 minutes. 70mL of isopropanol was then added and mixed. Titration was then performed on the liquid with 1 equivalent hydrochloric acid solution (factor F) with an indicator. The resulting titration value was set at V2mL. Then, the titration value obtained without the polyisocyanate sample was set to V1ml. The isocyanate group content (NCO%) of the polyisocyanate composition was then calculated from the following formula (mass%).
Isocyanate group content (% by mass) = (V1-V2) ×f×42/(w×1000) ×100)
[ Physical Property 2] (number average molecular weight and weight average molecular weight)
The number average molecular weight and the weight average molecular weight are the number average molecular weight and the weight average molecular weight of polystyrene as measured by Gel Permeation Chromatography (GPC) using the following apparatus.
(Measurement conditions)
Device HLC-802A manufactured by Tosoh Co., ltd
Column G1000 HXL. Times.1, manufactured by Tosoh Co., ltd
G2000 hxlx 1 root
G3000HXL x 1 root
Carrier tetrahydrofuran
Detection method differential refractometer
[ Physical Property 3] (average isocyanate functional group number)
The average isocyanate functional group number (average NCO number) of the polyisocyanate composition was determined by the following formula. In the formula, "Mn" represents a number average molecular weight, and the value measured in the above "physical property 2" is used. "NCO%" is a value calculated by using the above "physical property 1".
Average isocyanate functional group number= (mn×nco% ×0.01)/42
[ Physical Property 4] (glass transition temperature Tg)
Regarding the glass transition temperatures of the acrylic polyol and the crosslinkable functional group-containing polymer, the organic solvent and moisture in the acrylic polyol solution or the crosslinkable functional group-containing polymer solution are evaporated under reduced pressure, and then vacuum-dried, and the obtained material is measured at a temperature-rising rate of 5 ℃.
[ Production of cured film of polyisocyanate composition ]
The polyisocyanate compositions were applied to a release film using an applicator, stored for 168 hours at 23℃under a humidity environment of 65%, and heated for 24 hours at 50℃to obtain a cured film having a film thickness of 40. Mu.m.
[ Evaluation 1] (softness of cured film)
For the cured film, ke Nixi hardness (times) in the 23℃environment was measured by Ke Nixi durometer (Pendulum durometer (Pendulum HARDNESS TESTER) of BYK Gardner Co.) and Ke Nixi hardness of 60 times or less was evaluated as low hardness and good softness.
[ Production of coating film ]
The polyisocyanate compositions, the polyol and the acrylic polyol for producing the coating composition are mixed to obtain the coating composition. Each of the obtained coating compositions was applied to a release film by an applicator, cured at 90 ℃ for 30 minutes, and stored at 23 ℃ for 168 hours in a 65% humidity environment, to obtain a coating film.
[ Evaluation 2] (stress at 140% elongation)
For the obtained coating film, a test piece having a width of 10mm and a length of 100mm was set in a tensile tester at a clamp distance of 20mm, and a tensile test was performed at a speed of 20 mm/min to measure elongation and stress at an elongation of 140%. The elongation was 50% or more and the stress at 140% was 28MPa or less, and the elongation and the stress at 140% were evaluated as good.
[ Production of adhesive composition X ]
To 100 parts by mass of the acrylic polymer OH1, 0.5 part by mass of each polyisocyanate composition (1.0 part by mass of each of the polyisocyanate compositions PA1 to a5 and PA1 to a 11) and ethyl acetate were added to prepare an adhesive composition X having a solid content of 25% by mass.
[ Production of adhesive composition Y ]
To 100 parts by mass of the acrylic polymer OH2, 3 parts by mass of each polyisocyanate composition and ethyl acetate were added to prepare an adhesive composition Y having a solid content of 25% by mass.
[ Production of adhesive sheet 1] (production of adhesive sheet for 180-degree peel adhesion measurement)
The adhesive composition X or the adhesive composition Y was coated on a polyethylene terephthalate (PET) film having a thickness of 25 μm by an applicator in such a manner that the thickness after drying was 50. Mu.m, and dried at 130℃for 3 minutes. Thereafter, the resulting adhesive sheet was stored at 23℃under 50% RH for 7 days to obtain an adhesive sheet for 180-degree peel adhesion measurement.
[ Evaluation 3] (adhesion and cohesion)
Using the adhesive sheet obtained in "adhesive sheet production 1" above and using a SUS304BA steel sheet as an adherend, a test piece was pressed against the steel sheet by reciprocating a 2kg roller 1 time, cured at 23℃for 30 minutes, and then 180℃peel adhesion was measured at a speed of 300 mm/min using a tensile tester. The adhesion was evaluated to be good at 0.05N/20mm or more.
The adherend after peeling was evaluated as having good cohesive strength without leaving an adhesive layer (Table:. O.). A small amount of residual glue remaining on the surface of the adherend, which is 5% or less of the area of the bonded portion, was evaluated as Δ, a residual glue remaining on an area of more than 5% and less than 20 was evaluated as Δgood, and a residual glue remaining on an area of 20% or more was evaluated as x.
[ Production of adhesive sheet 2] (production of adhesive sheet for measuring gel fraction)
The adhesive composition X or the adhesive composition Y was applied to a release-treated PET film having a thickness of 38 μm by an applicator in such a manner that the thickness after drying was 50. Mu.m, and dried at 130℃for 3 minutes. Thereafter, the resultant sheet was stored at 23℃under 50% RH for 7 days to obtain an adhesive sheet for gel fraction measurement.
[ Evaluation 4] (curability)
The adhesive sheet obtained in "production of adhesive sheet 2" above was collected to an extent of 0.1g or more and 0.2g or less, wrapped with a net-like sheet, immersed in ethyl acetate for 1 week, and then dried at 120 ℃ for 2 hours. Next, the gel fraction (% by mass) was calculated by the following formula. The gel fraction was 20 mass% or more, and the curability was evaluated as good.
(Gel fraction) = (sample mass after drying)/(sample mass before ethyl acetate addition) ×100
[ Production of adhesive sheet 3] (production of adhesive sheet for haze value measurement)
The adhesive composition X or the adhesive composition Y was applied to a release-treated polyethylene terephthalate film having a thickness of 38. Mu.m, dried at 130℃for 3 minutes, and cured, and the formed adhesive layer having a thickness of 50. Mu.m was released from the release-treated polyethylene terephthalate film and then bonded to a glass having a haze value of 0.1%, to obtain an adhesive sheet for haze value measurement.
[ Evaluation 5] (transparency)
The haze of the adhesive sheet obtained in "production of adhesive sheet 3" described above was measured using a haze meter (HMG-2 DP) manufactured by Suga Test. The haze value was 2% or less, and the transparency was evaluated as good.
[ Preparation of resin composition ]
The polyisocyanate compositions and an acrylic polyol (trade name "Setalux1152" manufactured by Allnex corporation) were mixed so that the molar ratio of isocyanate groups to hydroxyl groups was 1.0, and further diluted with butyl acetate so that the solid content was 50 mass%. Then, a tin catalyst (trade name "NEOSTANN U-100", manufactured by Nito chemical Co., ltd.) was further mixed in an amount of 300 mass ppm with respect to the solid content to obtain each resin composition.
[ Evaluation 6] (compatibility with Main agent)
Each resin composition just prepared was maintained at an environment of-10 ℃ for 5 days. The state of the coating liquid was visually observed, and the evaluation was performed according to the following evaluation criteria.
(Evaluation criterion)
Transparent and uniform
Delta local turbidity
X, overall turbidity
[ Production of coating film ]
Each resin composition was coated on a polypropylene plate so as to have a film thickness of 30 μm, and dried by heating at 120 ℃ for 30 minutes. After that, each coating film was dried at 23 ℃ in a 50% humidity environment for 1 day, thereby producing each coating film.
[ Evaluation 7] (elongation at break at Low temperature)
The thus-produced coating film was cut into long strips to produce test pieces. Next, the test was carried out at a tensile test machine (Tensilon universal tester) at a test temperature of-10℃and a tensile speed of 20 mm/min, and the% elongation at break was measured. The elongation at break was evaluated according to the following evaluation criteria.
(Evaluation criterion)
Elongation at break of 150%
Elongation at break of 100% or more and less than 150%
Elongation at break less than 100%
[ Evaluation 8] (Low temperature Low stress Property (stress at 20% elongation))
The thus-produced coating film was cut into long strips to produce test pieces. Next, the test was carried out at a tensile speed of 20 mm/min at a test temperature of-10℃by being mounted on a tensile tester (Tensilon universal tester) in a manner of 20mm in length and 10mm in width. Based on the stress value at 20% elongation, the evaluation was performed according to the following evaluation criteria.
(Evaluation criterion)
Very small, less than 10MPa
O is more than 10MPa and less than 30MPa
X is 30MPa or more
[ Evaluation 9] (Normal temperature Low stress Property (stress at 75% elongation))
The thus-produced coating film was cut into a long strip shape, and a test piece was produced. Next, the test was carried out at a tensile speed of 20 mm/min at a test temperature of 23℃by being mounted on a tensile tester (Tensilon universal tester) in a manner of 20mm in length and 10mm in width. Based on the stress value at 75% elongation, the evaluation was performed according to the following evaluation criteria.
(Evaluation criterion)
Very small, less than 2MPa
2MPa or more and less than 5MPa
X is 5MPa or more
< Production of acrylic polyol >
Synthesis example 1-1 (preparation of acrylic polyol for producing coating composition)
29 Parts by mass of propylene glycol monomethyl ether was charged into a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet, and the temperature was raised to 112℃under nitrogen aeration. After the temperature reached 112 ℃, the introduction of nitrogen was stopped, and a mixture containing 22.3 parts by mass of 2-hydroxyethyl methacrylate, 8.0 parts by mass of methyl methacrylate, 26.1 parts by mass of butyl acrylate, 42.3 parts by mass of styrene, 1.3 parts by mass of acrylic acid and 2,2' -azobis (isobutyronitrile) was added dropwise over 5 hours. Then, after stirring for 3 hours while blowing nitrogen gas at 115 ℃, the mixture was cooled to 60 ℃, and a butyl acetate solution was charged to obtain a solution of an acrylic polyol for producing a coating composition having a solid content of 60% by mass. The glass transition temperature Tg of the acrylic polyol for producing the coating composition was 29.1 ℃, the hydroxyl value relative to the solid content of the resin was 139mgKOH/g, and the weight-average molecular weight Mw was 2.56X10 4.
< Synthesis of crosslinkable functional group-containing Polymer >
Synthesis examples 1 to 2 (Synthesis of acrylic Polymer OH 1)
Into a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a condenser, 97 parts by mass of 2-ethylhexyl acrylate (2 EHA) and 3 parts by mass of 4-hydroxybutyl acrylate (4-HBA) were charged, and 145 parts by mass of ethyl acetate as a solvent was charged. Then, 0.15 parts by mass of 2,2' -Azobisisobutyronitrile (AIBN) as a polymerization initiator was charged under stirring in a nitrogen atmosphere, and reacted at 63 ℃ for 8 hours. After the reaction, the reaction mixture was cooled to obtain an acrylic polymer OH1 having a solid content of 41.8% by mass. The glass transition temperature measured by removing the solvent of the acrylic polymer OH1 was-69℃and the weight average molecular weight was 8.3X10 5.
Synthesis examples 1 to 3 (Synthesis of acrylic Polymer OH 2)
97 Parts by mass of n-Butyl Acrylate (BA) and 3 parts by mass of 4-hydroxybutyl acrylate (4-HBA) were charged into a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet pipe and a condenser, and 145 parts by mass of ethyl acetate as a solvent was charged. Subsequently, 0.15 parts by mass of 2,2' -Azobisisobutyronitrile (AIBN) as a polymerization initiator was charged under stirring in a nitrogen atmosphere, and the reaction was performed at 63 ℃ for 8 hours. After the reaction, the reaction mixture was cooled to obtain an acrylic polymer OH2 having a solid content of 41.6% by mass. The glass transition temperature measured by removing the solvent of the acrylic polymer OH2 was-54℃and the weight average molecular weight was 7.8X10 5.
< Production of polyisocyanate composition 1>
[ Example 1-1] (production of polyisocyanate composition PA1-a 1)
Into a four-necked flask equipped with a thermometer, stirring blade, and reflux condenser, 100 parts by mass of HDI (hereinafter, referred to as "polyol A1" or simply "A1") was charged under a nitrogen flow, and while stirring 1.8 parts by mass of 2-functional polycaprolactone polyol A1 (hereinafter, referred to as "PLACCEL 220" by Dairy, trade name, number average molecular weight 2000) and 33 parts by mass of 3-functional polycaprolactone polyol B1 (hereinafter, referred to as "polyol B1" or simply "B1" by Dairy, trade name, PLACCEL 308, number average molecular weight 850) (the amount of hydroxyl groups of polyol A1 and polyol B1 was 10.2) were maintained at 95℃for 100 minutes. The reaction was stopped at a point in time when the yield was 41 mass%. After the reaction solution was filtered, unreacted HDI was removed by a thin film distillation apparatus to obtain a polyisocyanate composition PA1-a1.
Examples 1-2 to 1-13 and comparative examples 1-2 to 1-3 (production of polyisocyanate compositions PA1-a2 to PA1-a13 and PA1-b2 to PA1-b 3)
Each polyisocyanate composition was obtained in the same manner as in example 1-1 except that the compositions were set as shown in tables 1-1 to 1-2 and 1-4.
Examples 1 to 14 (production of polyisocyanate compositions PA1 to a 14)
100 Parts by mass of the polyisocyanate compositions PA1-a3 obtained in examples 1-3, 0.6 part by mass of methoxypolyethylene glycol (MPG-081, ethylene oxide repeating units: 15, manufactured by Japanese emulsifier Co., ltd.) and 0.08 part by mass of 2-ethylhexyl acid phosphate (JP-508T, manufactured by North-city chemical Co., ltd.) were mixed with a nitrogen gas stream in a four-necked flask equipped with a thermometer, stirring vanes and a reflux condenser, and stirred at 95℃for 2 hours to obtain polyisocyanate compositions PA1-a14.
Examples 1-15 to 1-18 (production of polyisocyanate compositions PA1-a15 to PA1-a18, PA1-a20 to PA1-a 21)
Each polyisocyanate composition was obtained in the same manner as in example 1-1 except that the composition was set as shown in Table 1-3. In addition, the reaction was stopped at the time when the yields of PA1-a20 and PA1-a21 reached 44% and 48%, respectively. Further, the treatment was carried out in the same manner as in example 1-1.
Examples 1 to 19 (production of polyisocyanate compositions PA1 to a 19)
Into a four-necked flask equipped with a thermometer, stirring blade, and reflux condenser, 100 parts by mass of HDI (hereinafter, referred to as "polyol A4" or simply "A4") was charged under a nitrogen flow, and while stirring 10 parts by mass of 2-functional polycaprolactone polyol A4 (manufactured by Dairy cellulo corporation, trade name "PLACCEL 220CPT", number average molecular weight 2000) and 32 parts by mass of 3-functional polycaprolactone polyol B1 (hereinafter, referred to as "polyol B1" or simply "B1") (manufactured by Dairy cellulo corporation, trade name "PLACCEL 308", number average molecular weight 850) (the amount of which the molar ratio of isocyanate groups of HDI to hydroxyl groups of polyol A1 and polyol B1 was 9.8) were maintained at 95℃for 100 minutes. The reaction was stopped at a point when the yield reached 41 mass%. After the reaction solution was filtered, unreacted HDI was removed by a thin film distillation apparatus to obtain a polyisocyanate composition. To a four-necked flask equipped with a thermometer, a stirring blade and a reflux condenser, 3 parts by mass (NCO/oh=24.4) of 2-functional polycaprolactone polyol A4 (trade name "placel 220CPT", number average molecular weight 2000, manufactured by macrocellule corporation) was mixed with 100 parts by mass of the obtained polyisocyanate under a nitrogen flow, and 0.060 parts by mass of JP-508t was added thereto, and the temperature in the reactor was kept at 105 ℃ for 120 minutes, thereby obtaining polyisocyanate compositions PA1-a19.
Comparative example 1-1 (production of polyisocyanate composition PA1-b 1)
Into a four-necked flask equipped with a thermometer, stirring blade and reflux condenser, 100 parts by mass of HDI and 8.9 parts by mass of trimethylolpropane were charged under a nitrogen flow, and the temperature in the reactor was kept at 75℃for 5 hours under stirring to carry out a urethanization reaction. After the reaction solution was filtered, unreacted HDI was removed using a thin film evaporator to obtain a polyisocyanate composition PA1-b1 containing an isocyanurate type polyisocyanate.
The physical properties of the polyisocyanate compositions 1 obtained in examples and comparative examples and the results of evaluation by the methods described above are shown in tables 1 to 4 below. In comparative example 1-1, when the stress was measured at an elongation of 140%, the elongation was not increased to 140% and the breaking stress was not measured at 72MPa, and thus the result was indicated as "-" in the table.
In tables 1 to 4, each abbreviation means the following compound.
(Polyol (A1))
A1-1:2 functional polycaprolactone polyol, trade name "PLACCEL 220", number average molecular weight 2000, manufactured by Daxillon Co., ltd
A1-2:2 functional polycaprolactone polyol, trade name "PLACCEL 230", number average molecular weight 3000, manufactured by Daxillon Co., ltd
A1-3:2 functional polycaprolactone polyol, trade name "PLACCEL 240", number average molecular weight 4000, manufactured by Daxiu Co., ltd
A1-4:2 functional polycaprolactone polyol, trade name "PLACCEL 220CPT", number average molecular weight 2000, manufactured by Daxiu Co., ltd
A1' -1 polytetramethylene ether glycol, mitsubishi chemical Co., ltd., trade name "PTMG1000", number average molecular weight 1000
A1' -2 polyether polyol, trade name "Exenol2020", manufactured by AGC Co., ltd., number average molecular weight 2000, hydroxyl value 55.8mg/KOH
A1' -3 polyether polyol, manufactured by AGC Co., ltd., trade name "Exenol4030", number average molecular weight 4000, hydroxyl value 42mg/KOH
A1' -4 polycarbonate diol, product of Asahi Kasei Co., ltd., trade name "T5652", number average molecular weight 2000, hydroxyl value 56.0mg/KOH
(Polyol (B1))
B1-1:3 functional polycaprolactone polyol, trade name "PLACCEL 308", number average molecular weight 850, manufactured by Daxillon Co., ltd
B1-2:3 functional polycaprolactone polyol, trade name "PLACCEL 312", number average molecular weight 1250, manufactured by Daxillon Co., ltd
B1-3:3 functional polycaprolactone polyol, trade name "PLACCEL 305", number average molecular weight 550, manufactured by Daxillon Co., ltd
B1' -1 Trimethylolpropane (TMP)
[ Table 1-1]
[ Tables 1-2]
[ Tables 1 to 3]
[ Tables 1 to 4]
In the case of polyisocyanate compositions PA1-a1 to PA1-a21 (examples 1-1 to 1-21) derived from 2 polyols having a number average molecular weight within a specific numerical range and having a weight average molecular weight of 1400 or more, the hardness and flexibility at the time of producing a cured film are low, the elongation and stress at the time of producing a coating film are good, and the adhesiveness, cohesive force, curability and transparency at the time of producing an adhesive sheet are excellent.
On the other hand, when the polyisocyanate composition PA1-b1 to PA1-b2 (comparative examples 1-1 to 1-2) derived from a diisocyanate and 1 polyol or the polyisocyanate composition PA1-b3 (comparative examples 1-3) derived from a diisocyanate and 2 polyols having a number average molecular weight outside a specific numerical range and having a weight average molecular weight of less than 1400, flexibility at the time of producing a cured film and adhesiveness, cohesive force, curability and transparency at the time of producing an adhesive sheet were not obtained.
< Production of polyisocyanate composition 2>
Examples 2 to 1
(Production of polyisocyanate composition PA2-a 1)
A4-neck flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was charged with 1000g of HDI and 496.0g of 3-functional polycaprolactone polyol (trade name "OD-X2588", manufactured by DIC Co., ltd., number average molecular weight 1250) under a nitrogen atmosphere, and the temperature in the reactor was kept at 100℃with stirring to carry out a urethanization reaction. After the reaction solution was filtered, unreacted HDI was removed using a thin film evaporator to obtain a polyisocyanate precursor. 100.0g of a polyisocyanate precursor was charged into a flask, 57.0g of polyoxypropylene diol (trade name "EXCENOL", number average molecular weight 4000, manufactured by AGC Co., ltd.) was charged, and the urethane reaction was carried out while maintaining the temperature in the reactor at 100℃with stirring, to obtain a polyisocyanate composition PA2-a1.
Examples 2-2 to 2-6
(Production of polyisocyanate compositions PA2-a 2-PA 2-a 6)
Each polyisocyanate composition was obtained in the same manner as in example 2-1 except that the compositions shown in Table 2-1 were used.
Examples 2 to 7
(Production of polyisocyanate composition PA2-a 7)
A4-neck flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was charged with 1000g of HDI, 150.0g of 3-functional polycaprolactone polyol (trade name "OD-X2735", number average molecular weight 500; manufactured by DIC Co., ltd.), 200.0g of polytetramethylene ether glycol (trade name "PTMG1000", number average molecular weight 1000", manufactured by Mitsubishi chemical Co., ltd.), and 300.0g of polyoxypropylene glycol (trade name" EXCENOL ", number average molecular weight 4000", manufactured by AGC Co., ltd.) under stirring, and the temperature in the reactor was maintained at 100℃to carry out the urethanization reaction. After the reaction solution was filtered, unreacted HDI was removed by using a thin film evaporator to obtain polyisocyanate compositions PA2-a6.
Examples 2 to 8 and comparative examples 2-1 to 2-3
(Production of polyisocyanate composition PA2-a8 and PA2-b1 to PA2-b 3)
Each polyisocyanate composition was obtained in the same manner as in examples 2 to 7 except that the compositions shown in Table 2-2 were used.
The physical properties of each of the obtained polyisocyanate compositions and the evaluation results using the methods described above are shown in tables 2-1 and 2-2.
The abbreviations in tables 2 to 1 and 2 to 2 represent the following compounds.
(Polycaprolactone polyol (A2))
A2: polycaprolactone polyols
OD-X-2735-3-functional polycaprolactone polyol, available from DIC Co., ltd., number average molecular weight 500
OD-X-2586 DIC Co., ltd., 3-functional polycaprolactone polyol, number average molecular weight 850
OD-X-2588 DIC Co., ltd., 3-functional polycaprolactone polyol, number average molecular weight 1250
(Polyether polyol (B2))
B2-1 polypropylene glycol
Excenol 510A, a polypropylene glycol, a number average molecular weight 4000, manufactured by AGC Co., ltd
Excenol 840A-840, polyoxypropylene triol, manufactured by AGC Co., ltd., number average molecular weight 6500
Excenol 1020A, polyoxypropylene diol, manufactured by AGC Co., ltd., number average molecular weight 1000
B2-2 other polyether polyol
PTMG1000, polytetramethylene ether glycol, number average molecular weight 1000, manufactured by Mitsubishi chemical Co., ltd
[ Table 2-1]
[ Table 2-2]
When the polyisocyanate compositions PA2-a1 to PA2-a8 (examples 2-1 to 2-8) derived from the diisocyanate, the polycaprolactone polyol (A2) and the polyether polyol (B2) and containing 20 parts by mass or more of polypropylene glycol per 100 parts by mass of the polyether polyol (B2), the compatibility with the main agent was excellent in a low temperature environment of about-10 ℃, and the elongation at break at a low temperature of about-10 ℃ and the low stress at a low temperature of about-10 ℃ and at a normal temperature of about 23 ℃ were excellent in the case of producing a coating film.
In the case of the polyisocyanate composition PA2-b1 (comparative example 2-1) derived from the diisocyanate and the polycaprolactone polyol (A2), the compatibility with the main agent was good in a low temperature environment of about-10 ℃, but the elongation at break at low temperature of about-10 ℃ and the low stress properties at low temperature of about-10 ℃ and at ordinary temperature of about 23 ℃ were poor when the film was formed.
In the case of the polyisocyanate composition PA2-B2 (comparative example 2-2) derived from the diisocyanate, the polycaprolactone polyol (A2) and the polyether polyol (B2) containing no polypropylene glycol, the elongation at break at low temperature of about-10 ℃ and the low stress at low temperature of about-10 ℃ and at normal temperature of about 23 ℃ at the time of producing the coating film were within the allowable range, but the compatibility with the main agent was poor in the low temperature environment of about-10 ℃.
In the case of the polyisocyanate composition PA2-B3 (comparative examples 2-3) derived from the diisocyanate, the polycaprolactone polyol (A2) and the polyether polyol (B2) and containing less than 20 parts by mass (10 parts by mass) of the polypropylene glycol per 100 parts by mass of the polyether polyol (B2), the elongation at break at low temperature of about-10 ℃ and the low stress at low temperature of about-10 ℃ and at normal temperature of about 23 ℃ at the time of producing the coating film were within the allowable range, but the compatibility with the base agent was poor in the low temperature environment of about-10 ℃.
Industrial applicability
According to the polyisocyanate composition 1 of the present embodiment, a cured film obtained by curing the polyisocyanate composition alone is excellent in flexibility, and an adhesive sheet excellent in adhesion, cohesion, curability and transparency can be obtained.
Further, the polyisocyanate composition 2 according to the present embodiment can provide a polyisocyanate composition which has good compatibility with a main agent in a low-temperature environment of about-10 ℃ and which is excellent in flexibility at a low temperature of about-10 ℃ and at a normal temperature of about 23 ℃ when a coating film is formed.

Claims (35)

1. A polyisocyanate composition derived from at least 1 diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, a 2-functional polyol (A1) having a number average molecular weight of 1500 or more, and a 3-functional or higher polyol (B1) having a number average molecular weight of 500 or more,
The molar ratio of isocyanate groups of the diisocyanate to hydroxyl groups of the polyol (A1) and the polyol (B1) is 2 to 30,
The weight average molecular weight of the polyisocyanate composition is 1400 or more,
The polyol (A1) and the polyol (B1) are polyester polyols.
2. The polyisocyanate composition according to claim 1, wherein the mass ratio of the alicyclic diisocyanate to the aliphatic diisocyanate is 0/100 or more and 30/70 or less.
3. The polyisocyanate composition according to claim 1 or 2, wherein the molar ratio of isocyanate groups of the diisocyanate to hydroxyl groups of the polyol (A1) and the polyol (B1) is 5 to 20.
4. The polyisocyanate composition according to claim 1 or 2, wherein the polyol (A1) has a number average molecular weight of 7000 or less.
5. The polyisocyanate composition according to claim 1 or 2, wherein the polyol (B1) has a number average molecular weight of 3000 or less.
6. The polyisocyanate composition according to claim 1 or 2, wherein the polyisocyanate composition has a weight average molecular weight of 100000 or less.
7. The polyisocyanate composition according to claim 1 or 2, wherein the mass ratio of the polyol (A1) to the polyol (B1), i.e., (A1)/(B1), is 0.1/99.9 or more and 99.9/0.1 or less, and
With respect to 100 parts by mass of the diisocyanate,
The content of the polyol (A1) is 0.1 to 250 parts by mass,
The content of the polyol (B1) is 1 to 190 parts by mass.
8. The polyisocyanate composition according to claim 7, wherein the mass ratio of (A1)/(B1) is 7/93 or more and 70/30 or less.
9. The polyisocyanate composition according to claim 7, wherein the content of the polyol (A1) is 1.7 parts by mass or more and 38 parts by mass or less.
10. The polyisocyanate composition according to claim 7, wherein the content of the polyol (B1) is 12 parts by mass or more and 50 parts by mass or less.
11. The polyisocyanate composition according to claim 1 or 2, wherein the polyisocyanate composition has an average isocyanate functional group number of 2 or more and 6 or less.
12. The polyisocyanate composition according to claim 1 or 2, wherein the polyisocyanate composition has an average isocyanate functional group number of 2.5 or more and 5.5 or less.
13. The polyisocyanate composition according to claim 1 or 2, wherein the polyisocyanate composition has an isocyanate group content of 1% by mass or more and 10% by mass or less.
14. The polyisocyanate composition according to claim 1 or 2, wherein the polyol (A1) and the polyol (B1) are polycaprolactone polyols.
15. A cured film which is obtained by applying the polyisocyanate composition according to any one of claims 1 to 14 to glass, storing the film in a humidity environment of 23 ℃ and 65% for 168 hours, heating the film at 50 ℃ for 24 hours, and then forming a film thickness of 40 μm,
The cured film has a Ke Nixi hardness of 60 times or less in an environment at 23 ℃.
16. A coating film which is obtained by curing a coating composition comprising the polyisocyanate composition according to any one of claims 1 to 14 and an acrylic polyol having a glass transition temperature of 29.1 ℃ and a hydroxyl value of 139mgKOH/g and a weight average molecular weight of 2.56X10 4 at 90 ℃ for 30 minutes and storing the coating composition in a 23 ℃ and 65% humidity environment for 168 hours, wherein the coating film has a film thickness of 40 μm,
In a tensile test in which a test piece having a width of 10mm and a length of 100mm of the coating film is set in a tensile tester with a clamp distance of 20mm and measured at a speed of 20 mm/min, the elongation of the coating film is 50% or more and the stress at an elongation of 140% is 28MPa or less.
17. An adhesive composition comprising the polyisocyanate composition according to any one of claims 1 to 14 and a crosslinkable functional group-containing polymer having a glass transition temperature of 0 ℃ or less.
18. The adhesive composition of claim 17, wherein the crosslinkable functional group-containing polymer is an acrylic polymer.
19. An adhesive sheet comprising:
A substrate, and
An adhesive layer on the substrate,
The adhesive layer comprises a cured product of the adhesive composition according to claim 17 or 18.
20. The adhesive sheet according to claim 19, wherein the thickness of the adhesive layer is 1 μm or more and 1000 μm or less.
21. The adhesive sheet according to claim 19 or 20, wherein the adhesive sheet having an adhesive layer of 50 μm thickness is formed by coating an adhesive composition on a peel-off-treated polyethylene terephthalate film of 38 μm thickness, drying the film at 130 ℃ for 3 minutes, and curing the film, wherein the adhesive sheet is covered with a net-like sheet after storage for 7 days at 23 ℃ in a 50% rh environment, immersing the film in ethyl acetate for 1 week at 23 ℃, drying the film at 120 ℃ for 2 hours after removal, and the gel fraction is 20 mass% or more and 99 mass% or less.
22. The adhesive sheet according to claim 19 or 20, wherein the adhesive sheet having a thickness of 50 μm and a width of 20mm and a length of 100mm is obtained by applying the adhesive composition to a polyethylene terephthalate film having a thickness of 50 μm, drying the film at 130 ℃ for 3 minutes and curing the film at 25 μm, and then pressing the film with a roll of SUS304BA once and back using a roll of 2kg after the adhesive sheet having a thickness of 50 μm and a width of 20mm and a length of 100mm is stored for 7 days at 23 ℃ and 50% rh, and curing the film at 23 ℃ for 30 minutes at a speed of 300 mm/min after curing the film at 23 ℃ and 180 ° peel adhesion of 0.05N/20mm or more and 55N/20mm or less.
23. The adhesive sheet according to claim 19 or 20, wherein the adhesive composition is applied to a release-treated polyethylene terephthalate film having a thickness of 38 μm and dried at 130 ℃ for 3 minutes to cure, and the adhesive layer having a thickness of 50 μm is peeled from the release-treated polyethylene terephthalate film and then attached to a glass having a haze value of 0.1% or less, whereby the adhesive sheet has a haze value of 2% or less as measured by a haze meter.
24. A coating film, film and adhesive composition, which is a resin film having a film thickness of 40 μm after curing a resin composition at 90 ℃ for 30 minutes and storing the resin composition in a 23 ℃ and 65% humidity environment for 168 hours, wherein the resin composition comprises the polyisocyanate composition according to any one of claims 1 to 14 and an acrylic polyol having a glass transition temperature of 0 ℃ to 100 ℃ and a hydroxyl value of 10mgKOH/g to 400mgKOH/g and a weight average molecular weight of 5.00X 10 3 to 1.0X 10 5,
In a tensile test in which a test piece having a width of 10mm and a length of 100mm of the resin film is set in a tensile tester with a clamp distance of 20mm and measured at a speed of 20 mm/min, the breaking stress of the resin film is 2.0MPa or more.
25. A coating film, film and adhesive composition, which is a resin film having a film thickness of 40 μm after curing a resin composition at 90 ℃ for 30 minutes and storing the resin composition in a 23 ℃ and 65% humidity environment for 168 hours, wherein the resin composition comprises the polyisocyanate composition according to any one of claims 1 to 14 and an acrylic polyol having a glass transition temperature of 0 ℃ to 100 ℃ and a hydroxyl value of 10mgKOH/g to 400mgKOH/g and a weight average molecular weight of 5.00X 10 3 to 1.0X 10 5,
In a tensile test in which a test piece having a width of 10mm and a length of 100mm of the resin film is set in a tensile tester with a clamp distance of 20mm and measured at a speed of 20 mm/min, the breaking stress of the resin film is 1.1 or more with respect to the stress at 140% elongation.
26. A polyisocyanate composition derived from at least 1 diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, a polycaprolactone polyol (A2), and a polyether polyol (B2),
Comprises 20 parts by mass or more of polypropylene glycol per 100 parts by mass of the polyether polyol (B2),
The polyisocyanate composition has an isocyanate group content of 3 to 8 mass%.
27. The polyisocyanate composition according to claim 26, wherein the polycaprolactone polyol (A2) has a number average molecular weight of 500 or more and 1500 or less, and
The polyether polyol (B2) has a number average molecular weight of 1000 to 7000.
28. The polyisocyanate composition of claim 27 wherein the polycaprolactone polyol (A2) has a number average molecular weight of 700 to 1500.
29. The polyisocyanate composition according to claim 27 or 28, wherein the polyether polyol (B2) has a number average molecular weight of 3000 or more and 6700 or less.
30. The polyisocyanate composition according to claim 27 or 28, wherein in the polyether polyol (B2), a mass ratio of polytetramethylene ether glycol to the polypropylene glycol is 0/100 or more and 60/40 or less.
31. The polyisocyanate composition according to claim 27 or 28, wherein in the polyether polyol (B2), a mass ratio of polytetramethylene ether glycol to the polypropylene glycol is 0/100 or more and 45/55 or less.
32. The polyisocyanate composition according to claim 26 or 27, wherein the molar ratio of isocyanate groups of the diisocyanate to hydroxyl groups of the polycaprolactone polyol (A2) and the polyether polyol (B2) is 2 or more and 10 or less.
33. The polyisocyanate composition according to claim 26 or 27, wherein the mass ratio of the polycaprolactone polyol (A2) to the polyether polyol (B2) is 10/90 or more and 90/10 or less.
34. A resin composition comprising the polyisocyanate composition according to any one of claims 26 to 33 and a polyol.
35. The resin composition of claim 34 which is an adhesive composition.
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