CN111349213B - Polyurethane resin composition and polishing pad - Google Patents

Polyurethane resin composition and polishing pad Download PDF

Info

Publication number
CN111349213B
CN111349213B CN201911275010.5A CN201911275010A CN111349213B CN 111349213 B CN111349213 B CN 111349213B CN 201911275010 A CN201911275010 A CN 201911275010A CN 111349213 B CN111349213 B CN 111349213B
Authority
CN
China
Prior art keywords
polyurethane resin
range
resin composition
polyol
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911275010.5A
Other languages
Chinese (zh)
Other versions
CN111349213A (en
Inventor
大仓雄介
前田亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp filed Critical DIC Corp
Publication of CN111349213A publication Critical patent/CN111349213A/en
Application granted granted Critical
Publication of CN111349213B publication Critical patent/CN111349213B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
    • B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
    • B24D3/28—Resins or natural or synthetic macromolecular compounds
    • B24D3/32—Resins or natural or synthetic macromolecular compounds for porous or cellular structure
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/054—Precipitating the polymer by adding a non-solvent or a different solvent
    • C08J2201/0542—Precipitating the polymer by adding a non-solvent or a different solvent from an organic solvent-based polymer composition
    • C08J2201/0544—Precipitating the polymer by adding a non-solvent or a different solvent from an organic solvent-based polymer composition the non-solvent being aqueous

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

The present invention provides a polyurethane resin composition comprising a polyurethane resin (X) which is prepared from a polyol (a), a polyisocyanate (b) and a chain extender (c), wherein the polyurethane resin (X) has an amorphous phase present in a range of 20 to 50% and a crystalline phase present in a range of 20 to 50% as measured by a pulse NMR measurement method. The present invention also provides a polishing pad comprising a porous body obtained from the polyurethane resin composition. The weight average molecular weight of the polyurethane resin (X) is preferably in the range of 12 to 30 ten thousand. The proportion of the polyisocyanate (b) used in the raw material constituting the polyurethane resin (X) is preferably in the range of 30 to 45 mass%.

Description

Polyurethane resin composition and polishing pad
Technical Field
The present invention relates to a polyurethane resin composition and a polishing pad.
Background
Polishing pads using polyurethane resin compositions are widely used in the fields of liquid crystal glass, hard disk glass, silicon wafers, semiconductors, and the like, where high surface flatness is required. Among them, a soft porous body is used in the final finish polishing, and the soft porous body is processed by a wet film forming method in which a polyurethane resin diluted with a solvent such as DMF (dimethylformamide) is solidified in water (for example, refer to patent document 1).
The characteristics required for the polishing pad based on the porous body include, for example, a high bulk modulus (=low compressibility) for maintaining flatness of the surface of the processed body, flexibility as a material for suppressing scratches on the surface, and fineness and uniformity (wet film forming property) of the porous unit for supporting maintenance and stable polishing of slurry (polishing liquid).
However, the low compressibility, flexibility and wet film forming property are the opposite physical properties, and for example, when attempting to reduce the compressibility of the polishing pad while paying attention to flatness, polyurethane resin is hardened and scratches are deteriorated. In addition, when the polyurethane resin is softened with importance attached to scratches, solidification in water becomes impossible to proceed rapidly, and uniformity of the porous unit is lost, resulting in unstable polishing. Thus, it is difficult to achieve both of the above physical properties at a high level.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2004-256738
Disclosure of Invention
Problems to be solved by the invention
The problem to be solved by the present invention is to provide a polyurethane resin composition having low compressibility, flexibility and excellent wet film forming property.
Means for solving the problems
The present invention provides a polyurethane resin composition comprising a polyurethane resin (X) which is prepared from a polyol (a), a polyisocyanate (b) and a chain extender (c), wherein the polyurethane resin (X) has an amorphous phase present in a range of 20 to 50% and a crystalline phase present in a range of 20 to 50% as measured by a pulse NMR measurement method.
The present invention also provides a polishing pad comprising a porous body based on the polyurethane resin composition.
ADVANTAGEOUS EFFECTS OF INVENTION
The polyurethane resin composition of the present invention is excellent in low compressibility, flexibility and wet film forming property.
Therefore, the polyurethane resin composition of the present invention can be suitably used as a polishing pad for finishing polishing having a porous body obtained by a wet film forming method.
Detailed Description
The polyurethane resin composition of the present invention contains a polyurethane resin (X) which is prepared from a polyol (a), a polyisocyanate (b) and a chain extender (c), and the polyurethane resin (X) has an amorphous phase present in a range of 20% to 50% and a crystalline phase present in a range of 20% to 50% as measured by a pulse NMR measurement method, in view of a high level of both low compressibility, flexibility and wet film forming properties.
In general, polyurethane resins (X) are known to be composed of a soft segment containing polyol (a) and a hard segment composed of urethane groups, urea groups, or the like derived from polyisocyanate (b) and chain extender (c). Here, the "amorphous phase" obtained by the pulse NMR measurement means the soft segment, and the "crystalline phase" means the hard segment. Accordingly, by setting the balance of the soft segment and the hard segment within the above range, it is possible to achieve a high level of both low compressibility, flexibility and wet film forming property. The method of measuring pulse NMR is described in examples described below.
In the pulse NMR measurement method, there is a region called "mesophase" in addition to the above-mentioned "amorphous phase" and "crystalline phase". This is a region where the soft segment and the hard segment are mixed, and the existence rate of the intermediate phase can be reduced by controlling the structure to be a better phase separation between the soft segment and the hard segment.
In the present invention, in order that the above-mentioned presence ratios of the above-mentioned "amorphous phase" and "crystalline phase" are positioned to be relatively high ratios and controlled to be in a numerical range that is simultaneously satisfied, it is important how to reduce the presence ratio of the "intermediate phase". As a technical idea that the existence ratio of the "amorphous phase" and the "crystalline phase" can be set to a relevant range, for example, there are: a technical idea of increasing the existence ratio of the soft segment by using a polyol (a) having a relatively high molecular weight as a raw material; a technical idea of using a polyisocyanate (b) having a relatively short chain length and a chain extender (c); technical ideas to facilitate formation of a phase separation structure by taking work in order of raw material reactions.
The ratio of the amorphous phase of the urethane resin (X) based on the pulse NMR measurement is preferably in the range of 25% to 40% from the viewpoint of obtaining more excellent low compressibility and flexibility, and the ratio of the crystalline phase is preferably in the range of 25% to 40%.
Examples of the polyol (a) include polyester polyol, polyether polyol, polycarbonate polyol, polyacrylic polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, and dimer diol. These polyols may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining more excellent wet film forming properties, 1 or more selected from the group consisting of polyester polyols, polyether polyols and polycarbonate polyols are preferably used, and polypropylene glycol and/or polytetramethylene glycol are preferable as the polyether polyols.
The number average molecular weight of the polyol (a) is preferably 500 to 100000, more preferably 700 to 10000, and even more preferably 800 to 5000. The number average molecular weight of the polyol (a) is a value measured by Gel Permeation Chromatography (GPC).
The proportion of the polyol (a) used in the raw material constituting the polyurethane resin (X) is preferably in the range of 35 to 65 mass%, more preferably in the range of 40 to 60 mass%.
As the polyisocyanate (b), for example, aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; alicyclic polyisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, and norbornene diisocyanate; aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimide diphenylmethane polyisocyanate. These polyisocyanates may be used alone or in combination of two or more. From the viewpoint of obtaining more excellent wet film forming properties, it is preferable to use an aromatic polyisocyanate, and diphenylmethane diisocyanate is more preferable.
The proportion of the polyisocyanate (b) used in the raw material constituting the polyurethane resin (X) is preferably in the range of 30 to 45 mass%, more preferably in the range of 35 to 40 mass%, from the viewpoint of obtaining further excellent low compressibility, flexibility and wet film forming property.
The chain extender (c) is a chain extender having a molecular weight of less than 500 (preferably in the range of 50 to 450), and examples thereof include chain extenders having an amino group such as ethylenediamine, 1, 2-propylenediamine, 1, 6-hexamethylenediamine, piperazine, 2, 5-dimethylpiperazine, isophoronediamine, 1, 2-cyclohexanediamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, 4' -dicyclohexylmethane diamine, 3' -dimethyl-4, 4' -dicyclohexylmethane diamine, and hydrazine; chain extenders having hydroxyl groups such as 2, 4-dimethyl-1, 5-pentanediol, 2, 3-dimethyl-1, 5-pentanediol, 2-ethyl-1, 5-pentanediol, 2-methyl-1, 6-hexanediol, 3-methyl-1, 6-hexanediol, 1, 7-nonanediol, 2-ethyl-1, 6-hexanediol, 2-methyl-1, 7-nonanediol, 3-methyl-1, 7-nonanediol, 4-methyl-1, 7-nonanediol, 1, 8-octanediol, 2-methyl-1, 8-octanediol, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, 3-methyl-1, 8-octanediol, 4-methyl-1, 8-octanediol, 1, 10-decanediol, 2-methyl-1, 10-decanediol, 3-methyl-1, 10-decanediol, 4-methyl-1, 10-decanediol, 1, 11-undecanediol, trimethylolpropane, and the like. These chain extenders may be used alone or in combination of two or more. The molecular weight of the chain extender (c) represents the formula weight calculated based on the chemical formula.
The proportion of the chain extender (c) used in the raw material constituting the polyurethane resin (X) is preferably in the range of 5 to 20 mass%, more preferably in the range of 5 to 15 mass%.
The method for producing the polyurethane resin (X) includes, for example, a method in which the polyol (a), the polyisocyanate (b), and the chain extender (c) are added and reacted with each other. These reactions are carried out, for example, at a temperature of 50℃to 100℃for 3 hours to 10 hours. The reaction may be carried out in an organic solvent (Y) described later.
The weight average molecular weight of the urethane resin (X) is preferably in the range of 12 to 30 tens of thousands, more preferably in the range of 14 to 25 tens of thousands, from the viewpoint of obtaining further excellent low compressibility and wet film forming property. The weight average molecular weight of the polyurethane resin (X) is a value measured by Gel Permeation Chromatography (GPC).
The content of the urethane resin (X) in the urethane resin composition is in the range of 5 to 80 mass%.
As the organic solvent (Y), for example, ketone solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl N-propyl ketone, acetone, methyl isobutyl ketone, and the like can be used; ester solvents such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, and sec-butyl acetate; alcohol solvents such as methanol, ethanol, isopropanol, butanol, etc. These organic solvents may be used alone or in combination of two or more.
The polyurethane resin composition of the present invention contains the polyurethane resin (X) as an essential component, and may contain other additives as required.
Examples of the other additives include pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, defoamers, dispersants, penetrants, surfactants, fillers, mold inhibitors, antibacterial agents, ultraviolet absorbers, antioxidants, weather-resistant stabilizers, fluorescent brighteners, antioxidants, and thickeners. These additives may be used alone or in combination of two or more.
The film formed from the polyurethane resin composition preferably has a 100% modulus obtained in a tensile test under a crosshead speed of 300 mm/min, and from the viewpoint of obtaining more excellent flexibility, it is preferably in the range of 7 to 20MPa, more preferably in the range of 9 to 16 MPa. The method for measuring 100% modulus of the coating film is represented by the method according to JIS K: the values measured by the method of 1995 are specifically described in examples described later.
Next, a method for producing a porous body by a wet film forming method using the polyurethane resin composition will be described.
The wet film forming method means: and a method in which the polyurethane resin composition is applied or impregnated onto the surface of a substrate, and then water or steam is brought into contact with the applied surface or the impregnated surface, thereby solidifying the polyurethane resin (X) to produce a porous body.
As a substrate to which the polyurethane resin composition is applied, for example, a substrate composed of a nonwoven fabric, a woven fabric, or a woven fabric; resin films, and the like. As a material constituting the base material, for example, a chemical fiber such as a polyester fiber, a nylon fiber, an acrylic fiber, a polyurethane fiber, an acetate fiber, a rayon fiber, or a polylactic acid fiber; cotton, hemp, cicada silk, wool, blends thereof, and the like.
The surface of the base material may be subjected to antistatic treatment, mold release treatment, hydrophobic treatment, water absorption treatment, antibacterial/deodorant treatment, antibacterial treatment, ultraviolet blocking treatment, and the like, as required.
Examples of the method of coating or impregnating the surface of the substrate with the polyurethane resin composition include a gravure coating method, a doctor blade coating method, a tube coating method, and a comma coating method. In this case, the amount of the organic solvent (Y) used may be adjusted as needed in order to adjust the viscosity of the polyurethane resin composition to improve the coating workability.
The thickness of the dried film of the polyurethane resin composition applied or impregnated by the above method is, for example, in the range of 0.5mm to 5mm, preferably in the range of 0.5mm to 3 mm.
Examples of the method of bringing water or water vapor into contact with the coated surface formed by coating or impregnating the polyurethane resin composition include: a method of immersing a substrate provided with a coating layer or an impregnating layer containing the polyurethane resin composition in a water bath; a method of spraying water on the coated surface using spraying or the like. The impregnation may be carried out in a water bath at 5 to 60℃for 2 to 20 minutes, for example.
The porous body is preferably washed with water or warm water at normal temperature, and the surface is preferably subjected to extraction to remove the organic solvent (Y) and then dried. The washing is preferably performed with water at 5 to 60 ℃ for 20 to 120 minutes, and the water used for washing is preferably replaced with water more than 1 time or continuously replaced with running water. Preferably, the drying is performed for 10 minutes to 60 minutes using a dryer or the like adjusted to 80 ℃ to 120 ℃.
The porous body has a long spindle-shaped or tear-drop-shaped porous structure in the thickness direction of the surface. The size of the hole is preferably in the range of 1 μm to 70 μm in diameter at the portion having the largest width in the plane direction. The thickness of the porous body is preferably 0.4 to 1.2mm, more preferably 0.4 to 1mm, in terms of use in polishing pads and the like.
As described above, the polyurethane resin composition of the present invention is excellent in low compressibility, flexibility and wet film forming property.
Therefore, the polyurethane resin composition of the present invention can be suitably used as a polishing pad for finishing polishing having a porous body obtained by a wet film forming method.
Examples
Hereinafter, the present invention will be described in more detail using examples.
Example 1
Into a four-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 100 parts by mass of a polyester polyol (reactant of ethylene glycol and adipic acid, number average molecular weight: 2000, hereinafter abbreviated as "PEs (1)"), 20 parts by mass of 1, 4-butanediol (hereinafter abbreviated as "BG"), 564 parts by mass of N, N-dimethylformamide (hereinafter abbreviated as "DMF"), and 68 parts by mass of 4,4' -diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") were charged, and the reaction was carried out under stirring at 60 ℃ for 6 hours, followed by charging 1 part by mass of isopropyl alcohol, and further stirring at 60 ℃ for 1 hour, thereby obtaining a polyurethane resin composition. The polyurethane resin had a weight average molecular weight of 188100.
Examples 2 to 5 and comparative examples 1 to 3
As shown in tables 1 and 2, polyurethane resin compositions were obtained in the same manner as in example 1, except that the types and amounts of the materials were changed.
[ method for measuring number average molecular weight ]
The number average molecular weight of the polyol and the weight average molecular weight of the polyurethane resin used in examples and comparative examples represent values measured by Gel Permeation Chromatography (GPC) under the following conditions.
Measurement device: high-speed GPC apparatus (HLC-8220 GPC, manufactured by Tosoh Co., ltd.)
Chromatographic column: the following columns manufactured by Tosoh corporation were used in series.
"TSKgel G5000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G4000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G3000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G2000" (7.8 mmI.D..times.30 cm). Times.1 root
A detector: RI (differential refractometer)
Column temperature: 40 DEG C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100. Mu.L (tetrahydrofuran solution with sample concentration of 0.4% by mass)
Standard sample: calibration curves were made using standard polystyrene as described below.
(Standard polystyrene)
TSKgel Standard polystyrene A-500 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-1000 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-2500 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-5000 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-1 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-2 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-4 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-10 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-20 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-40 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-80 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-128 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-288 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-550 manufactured by Tosoh Co., ltd "
[ method for measuring 100% modulus ]
A coating film was produced by adding 40 parts by mass of DMF to 100 parts by mass of the polyurethane resin compositions obtained in examples and comparative examples, and applying the mixture to a flat release paper (manufactured by Lintec Co., ltd. "EK-100D") so that the film thickness after drying became 30. Mu.m, drying at 90℃for 2 minutes, and further drying at 120℃for 2 minutes. Next, the obtained film was cut into a long shape having a width of 5mm and a length of 70mm, and 100% modulus (MPa) was measured at a crosshead speed of 300 mm/min using an Autograph (AG-1 KNX, manufactured by Shimadzu corporation).
[ method of measuring pulse NMR ]
The presence ratio (%) of an amorphous phase, a crystalline phase and an intermediate phase was measured by a pulse NMR (nuclear magnetic resonance) measurement method using the following conditions for the film obtained in the above [100% modulus measurement method ].
The measuring method comprises the following steps: pulse NMR measurement-based "Solid Echo" method
Measurement device: JNM-MU25 manufactured by Japanese electronics Co., ltd "
Measurement conditions: 1H90 pulse: 2.9 mu S
Repetition time: 3s
Accumulating times: 32 times
Measuring temperature: 27 DEG C
[ method for evaluating Wet film Forming Property ]
100 parts by mass of the obtained polyurethane resin composition was coated on a polyethylene terephthalate (PET) film so as to have a thickness of 1mm, and then immersed in water at 25℃for 10 minutes to solidify it. Then, the film was washed in warm water at 50℃for 60 minutes and left to stand in a dryer at 100℃for 30 minutes, thereby obtaining a processed film. The cross-sectional state of the obtained processed film was observed by a scanning electron microscope "JSM-IT500" (magnification: 100 times) manufactured by japan electronics corporation, and the cell shape (fineness, uniformity) was confirmed, and if the cell having the maximum lateral width of 70 μm or less was 60% or more of the whole, the cell was evaluated as "o", and the other was evaluated as "x".
[ method of evaluating compression Rate ]
The compression ratio of the processed film obtained in the above [ method for evaluating wet film formability ] was evaluated in accordance with JISL-1021-6. Specifically, for "thickness under standard pressure" after applying an initial load of 2kpa for 30 seconds: t0 "is measured, and the" thickness under specific pressure "after 30 seconds of the load of 98kPa as a final load is applied: t1 "was measured and applied to the following equation to calculate the compression ratio.
Compression ratio (%) =100× (t 0-t 1)/t 0
The compression ratio thus obtained was 20% or less, and the other was evaluated as "o".
[ method for evaluating softness ]
The processed film obtained in the above [100% modulus measuring method ] was measured for storage modulus (E ') at 23℃by dynamic viscoelasticity analysis in accordance with JIS K7244-1999 under the following conditions, and the processed film was evaluated as "O" when E' was 200MPa or less, and otherwise evaluated as "X".
Measurement device: viscoelasticity spectrometer (SII technology company's DMS 6100')
Temperature range: 100-250 DEG C
Heating rate: 5 ℃/min
Frequency 1Hz, stretching mode
[ Table 1]
[ Table 2 ]
Abbreviations in tables 1 to 2 are explained.
"PEs (2)": 1, 4-butanediol and adipic acid, number average molecular weight: 2000
"PEs (3)": the reactants of ethylene glycol, 1, 4-butanediol and adipic acid, number average molecular weight: 2000
"PEs (4)": 1, 6-hexanediol and adipic acid, number average molecular weight: 2000
"PEs (5)": 1, 4-butanediol and adipic acid, number average molecular weight: 1000
"PTMG": polytetramethylene glycol, number average molecular weight: 2000
"EG": ethylene glycol
The amounts used in the tables represent parts by mass.
The proportion (mass%) of the polyisocyanate (b) used in the constituent raw materials represents a value obtained by rounding the first decimal point.
The polyurethane resin composition of the present invention is excellent in low compressibility, flexibility and wet film forming property.
On the other hand, comparative example 1 is an embodiment in which the presence ratio of the amorphous phase is lower than the range defined in the present invention and the presence ratio of the crystalline phase exceeds the range defined in the present invention, and the flexibility is poor.
Comparative example 2 is an embodiment in which the presence ratio of the amorphous phase is lower than the range defined in the present invention, and the low compressibility is poor.
Comparative example 3 is an embodiment in which the presence ratio of the amorphous phase exceeds the range defined in the present invention and the presence ratio of the crystalline phase is lower than the range defined in the present invention, and the low compressibility and wet film forming property are poor.

Claims (3)

1. A polyurethane resin composition comprising a polyurethane resin X, wherein the polyurethane resin X is prepared from a polyol a, a polyisocyanate b and a chain extender c,
the polyol a comprises a polyester polyol,
the polyester polyol is at least one selected from the group consisting of a reactant of ethylene glycol and adipic acid, a reactant of 1, 4-butanediol and adipic acid, a reactant of ethylene glycol and 1, 4-butanediol and adipic acid, and a reactant of 1, 6-hexanediol and adipic acid,
the number average molecular weight of the polyol a is in the range of 2000 to 5000,
the polyisocyanate b is diphenylmethane diisocyanate,
the chain extender c is ethylene glycol or 1, 4-butanediol,
the weight average molecular weight of the polyurethane resin X is in the range of 14 to 25 ten thousand,
the polyol a is used in a proportion of 40 to 65 mass% in the raw material constituting the polyurethane resin X,
the polyisocyanate b is used in a proportion of 30 to 45 mass% in the raw material constituting the polyurethane resin X,
the proportion of the chain extender c used in the raw material constituting the polyurethane resin X is in the range of 5 to 20 mass%,
the amorphous phase of the polyurethane resin X was present in a range of 20% to 50% and the crystalline phase was present in a range of 20% to 50% as measured based on pulse NMR measurement.
2. A polishing pad comprising a porous body obtained based on the polyurethane resin composition according to claim 1.
3. The polishing pad according to claim 2, which is used for finish polishing.
CN201911275010.5A 2018-12-20 2019-12-12 Polyurethane resin composition and polishing pad Active CN111349213B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-238336 2018-12-20
JP2018238336A JP7302168B2 (en) 2018-12-20 2018-12-20 Urethane resin composition and polishing pad

Publications (2)

Publication Number Publication Date
CN111349213A CN111349213A (en) 2020-06-30
CN111349213B true CN111349213B (en) 2024-02-06

Family

ID=71120906

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911275010.5A Active CN111349213B (en) 2018-12-20 2019-12-12 Polyurethane resin composition and polishing pad

Country Status (4)

Country Link
JP (1) JP7302168B2 (en)
KR (1) KR20200077424A (en)
CN (1) CN111349213B (en)
TW (1) TW202033597A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111607060A (en) * 2020-07-13 2020-09-01 扬州雷应精密科技有限公司 High-entropy polyurethane and preparation method thereof
JP2022153966A (en) * 2021-03-30 2022-10-13 富士紡ホールディングス株式会社 Abrasive pad and method for producing abrasive pad

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10110025A (en) * 1996-10-04 1998-04-28 Dainippon Ink & Chem Inc Thermoplastic polyurethane resin composition
CN1407606A (en) * 2001-08-24 2003-04-02 株式会社罗捷士井上 Grinding pad
JP2004256738A (en) * 2003-02-27 2004-09-16 Dainippon Ink & Chem Inc Resin composition for polishing cloth and polishing cloth composed of the composition
JP2005015643A (en) * 2003-06-26 2005-01-20 Dic Bayer Polymer Ltd Thermoplastic polyurethane resin composition and molded product
JP2005306199A (en) * 2004-04-21 2005-11-04 Dainippon Ink & Chem Inc Urethane composition for runflat tire, and support body for runflat tire using it
JP2007238783A (en) * 2006-03-09 2007-09-20 Mitsui Chemicals Inc Foaming body
TW201033237A (en) * 2008-09-30 2010-09-16 Dainippon Ink & Chemicals Polyurethane resin composition for polishing pads, polyurethane polishing pads and method for making polyurethane polishing pads
JP2010240777A (en) * 2009-04-06 2010-10-28 Nitta Haas Inc Polishing pad
CN102159609A (en) * 2009-06-29 2011-08-17 Dic株式会社 Two-pack urethane resin composite for use in an abrasive pad, polyurethane abrasive pad, and method for manufacturing a polyurethane abrasive pad
JP2012102182A (en) * 2010-11-08 2012-05-31 Dic Corp Urethane resin composition for wet film formation, porous body and polishing pad obtained using the resin composition, and methods of manufacturing them
CN103563056A (en) * 2011-04-15 2014-02-05 富士纺控股株式会社 Polishing pad and manufacturing method therefor
CN103906778A (en) * 2011-09-29 2014-07-02 陶氏环球技术有限责任公司 Viscoelastic foam
CN103930975A (en) * 2011-10-18 2014-07-16 富士纺控股株式会社 Polishing pad and method for producing same
CN105745261A (en) * 2013-12-25 2016-07-06 Dic株式会社 Porous body and polishing pad
JP2017002145A (en) * 2015-06-08 2017-01-05 Dic株式会社 Urethane resin composition and leather-like sheet
CN107107307A (en) * 2015-03-30 2017-08-29 霓达哈斯股份有限公司 Grinding pad
CN107286313A (en) * 2017-07-10 2017-10-24 陕西瑞盛生物科技有限公司 A kind of degradable polyurethane foam and its application

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10110025A (en) * 1996-10-04 1998-04-28 Dainippon Ink & Chem Inc Thermoplastic polyurethane resin composition
CN1407606A (en) * 2001-08-24 2003-04-02 株式会社罗捷士井上 Grinding pad
JP2004256738A (en) * 2003-02-27 2004-09-16 Dainippon Ink & Chem Inc Resin composition for polishing cloth and polishing cloth composed of the composition
JP2005015643A (en) * 2003-06-26 2005-01-20 Dic Bayer Polymer Ltd Thermoplastic polyurethane resin composition and molded product
JP2005306199A (en) * 2004-04-21 2005-11-04 Dainippon Ink & Chem Inc Urethane composition for runflat tire, and support body for runflat tire using it
JP2007238783A (en) * 2006-03-09 2007-09-20 Mitsui Chemicals Inc Foaming body
TW201033237A (en) * 2008-09-30 2010-09-16 Dainippon Ink & Chemicals Polyurethane resin composition for polishing pads, polyurethane polishing pads and method for making polyurethane polishing pads
JP2010240777A (en) * 2009-04-06 2010-10-28 Nitta Haas Inc Polishing pad
CN102159609A (en) * 2009-06-29 2011-08-17 Dic株式会社 Two-pack urethane resin composite for use in an abrasive pad, polyurethane abrasive pad, and method for manufacturing a polyurethane abrasive pad
JP2012102182A (en) * 2010-11-08 2012-05-31 Dic Corp Urethane resin composition for wet film formation, porous body and polishing pad obtained using the resin composition, and methods of manufacturing them
CN103563056A (en) * 2011-04-15 2014-02-05 富士纺控股株式会社 Polishing pad and manufacturing method therefor
CN103906778A (en) * 2011-09-29 2014-07-02 陶氏环球技术有限责任公司 Viscoelastic foam
CN103930975A (en) * 2011-10-18 2014-07-16 富士纺控股株式会社 Polishing pad and method for producing same
CN105745261A (en) * 2013-12-25 2016-07-06 Dic株式会社 Porous body and polishing pad
CN107107307A (en) * 2015-03-30 2017-08-29 霓达哈斯股份有限公司 Grinding pad
JP2017002145A (en) * 2015-06-08 2017-01-05 Dic株式会社 Urethane resin composition and leather-like sheet
CN107286313A (en) * 2017-07-10 2017-10-24 陕西瑞盛生物科技有限公司 A kind of degradable polyurethane foam and its application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
泄气保用轮胎用聚氨酯内支撑体胶料配方;李汉堂;《现代橡胶技术》;20081015(第05期);10-13 *

Also Published As

Publication number Publication date
KR20200077424A (en) 2020-06-30
JP7302168B2 (en) 2023-07-04
CN111349213A (en) 2020-06-30
TW202033597A (en) 2020-09-16
JP2020100688A (en) 2020-07-02

Similar Documents

Publication Publication Date Title
CN107922562B (en) Moisture-curable hot-melt polyurethane composition, method for producing foamed cured product thereof, synthetic leather, and method for producing same
CN109722918B (en) Polyurethane resin composition, coating film, and synthetic leather
CN111349213B (en) Polyurethane resin composition and polishing pad
WO2015098271A1 (en) Porous body and polishing pad
US11111353B2 (en) Porous-object production method
WO2014030452A1 (en) Urethane resin composition, leather-like sheet, and laminate
CN116355178A (en) Wet film forming material
CN114539500A (en) Wet film-forming material
JP6528915B1 (en) Urethane resin composition, film, and synthetic leather
KR102499140B1 (en) Urethane resin composition and method for producing porous body
KR102216416B1 (en) Manufacturing method of porous body
JPWO2020116304A1 (en) Synthetic leather
JP6828854B1 (en) Urethane resin composition and synthetic leather
KR102298393B1 (en) Manufacturing method of porous body
JP2023044910A (en) Urethane resin composition and method for producing porous body
TW202144447A (en) Carbamate resin composition and synthetic leather characterized by comprising a carbamate resin that uses a polyol containing a polycarbonate polyol, a chain extender other than the polyol and a polyisocyanate as essential raw materials
WO2016185803A1 (en) Porous material and polishing pad
JP2022154112A (en) Synthetic leather

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant