TWI461450B - Two-package curing type polyurethane resin composition and methods for making urethane molded products for polishing pads - Google Patents
Two-package curing type polyurethane resin composition and methods for making urethane molded products for polishing pads Download PDFInfo
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- TWI461450B TWI461450B TW098132877A TW98132877A TWI461450B TW I461450 B TWI461450 B TW I461450B TW 098132877 A TW098132877 A TW 098132877A TW 98132877 A TW98132877 A TW 98132877A TW I461450 B TWI461450 B TW I461450B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/70—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
- C08G18/7685—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing two or more non-condensed aromatic rings directly linked to each other
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
本發明係關於一種用於如玻璃基板、矽晶圓、半導體元件(semiconductor device)等之要求高度表面平坦性的玻璃材料之生產的熱硬化性胺基甲酸酯(TSU)型之硏磨墊用2液型胺基甲酸酯樹脂組成物、使用它而成之聚胺基甲酸酯硏磨墊、及該聚胺基甲酸酯硏磨墊之製法。BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a thermosetting urethane (TSU) type honing pad for use in the production of glass materials requiring high surface flatness such as glass substrates, tantalum wafers, semiconductor devices, and the like. A method for preparing a composition of a two-component urethane resin, a polyurethane lining pad using the same, and the urethane pad.
以往，液晶顯示器(LCD)用玻璃基板、硬碟(HDD)用玻璃基板、記錄裝置用玻璃碟片、光學用透鏡、矽晶圓、半導體元件等之要求高度表面平坦性的玻璃材料的一般製造上，係首先進行使用胺基甲酸酯樹脂製之硏磨墊的「粗加工步驟」，接著進行使用硏磨布之「精加工步驟」，以進行精密硏磨。Conventionally, general manufacturing of glass materials requiring high surface flatness such as a glass substrate for a liquid crystal display (LCD), a glass substrate for a hard disk (HDD), a glass disk for a recording device, an optical lens, a germanium wafer, and a semiconductor element. In the above, the "roughing step" of using the lining pad made of urethane resin is first performed, followed by the "finishing step" using the honing cloth for precision honing.
作為可用於玻璃硏磨之熱硬化性胺基甲酸酯樹脂製的硏磨墊之方法，迄今已有例如組合含有異氰酸酯基末端胺基甲酸酯預聚物之主劑與硬化劑之所謂的2液型胺基甲酸酯樹脂組成物之各種提案。As a method of using a honing pad made of a thermosetting urethane resin for glass honing, there has been a so-called combination of a main component containing a isocyanate group-terminated urethane prepolymer and a hardener. Various proposals for a two-component urethane resin composition.
例如，已知一種玻璃硏磨聚胺基甲酸酯墊用之2液型組成物，其係由含有異氰酸酯基末端胺基甲酸酯預聚物之主劑，與含有異氰酸酯基反應性化合物、作為發泡劑的水、無機硏磨劑及觸媒之硬化劑所構成的玻璃硏磨聚胺基甲酸酯墊用2液型組成物，前述預聚物係分別使用至少甲苯二異氰酸酯(TDI)、聚(四亞甲基醚)乙二醇(PTMG)及聚己內酯三醇(PCL)，在混合PTMG與PCL的情況下使平均官能基數成為2.1~2.7之範圍，來使其反應而得之異氰酸酯基末端胺基甲酸酯預聚物，且前述異氰酸酯基反應性化合物係至少由4,4’-二胺基-3,3’-二氯二苯基甲烷與聚(四亞甲基醚)乙二醇所構成。該2液型組成物之預聚物為低黏度，混合成形時之泡沫、氣孔減低，可得均勻的氣泡，此外，藉由聚醇混合物之平均官能基數的適性化，能夠抑制因硏磨加工時發熱所導致的硏磨墊之硬度降低(例如，參照專利文獻1)。For example, a two-component composition for a glass honing polyurethane pad is known which comprises a main component containing an isocyanate-terminated urethane prepolymer and an isocyanate-containing reactive compound. A two-liquid type composition for a glass honing polyurethane pad composed of water, an inorganic honing agent and a curing agent for a catalyst as a foaming agent, wherein the prepolymer is at least toluene diisocyanate (TDI) ), poly(tetramethylene ether) glycol (PTMG) and polycaprolactone triol (PCL), in the case of mixing PTMG and PCL, the average functional group number is in the range of 2.1 to 2.7 to react And an isocyanate-terminated urethane prepolymer, and the aforementioned isocyanate-reactive compound is at least 4,4'-diamino-3,3'-dichlorodiphenylmethane and poly(four Methyl ether) ethylene glycol. The prepolymer of the two-component composition has a low viscosity, and the foam and pores in the mixed molding are reduced to obtain uniform bubbles, and further, the aging of the polyhydric alcohol mixture can suppress the honing process. The hardness of the honing pad caused by the heat generation is lowered (for example, refer to Patent Document 1).
然而，使用專利文獻1記載之2液型組成物所構成的玻璃硏磨聚胺基甲酸酯墊來進行加工物的硏磨時，由於硏磨墊與加工物之間所產生的摩擦熱，硏磨墊表面之溫度係顯著上昇，且前述樹脂組成在漿液或水溶液的存在下伴隨著顯著的溫度上昇，硏磨墊之耐熱水性惡化，因此硏磨墊的硬度(彈性模數)改變，而有對要求高度表面平坦性之玻璃材料的平坦化加工造成不良影響之問題。However, when the honing of the workpiece is performed using the glass honing polyurethane pad composed of the two-liquid composition described in Patent Document 1, the frictional heat generated between the honing pad and the workpiece is caused by the friction heat generated by the honing pad and the workpiece. The temperature of the surface of the honing pad is significantly increased, and the resin composition is accompanied by a significant temperature rise in the presence of a slurry or an aqueous solution, and the hot water resistance of the honing pad is deteriorated, so that the hardness (elastic modulus) of the honing pad is changed, and There is a problem of adversely affecting the planarization processing of a glass material requiring high surface flatness.
如上所述，將聚異氰酸酯與聚胺基氯苯基甲烷化合物之反應性控制到作業上沒有問題的程度、各種硏磨性能優異之硏磨墊用2液型胺基甲酸酯樹脂組成物、及使用它而成之聚胺基甲酸酯硏磨墊的開發係迫切期望。As described above, the reactivity of the polyisocyanate and the polyaminochlorophenylmethane compound is controlled to the extent that there is no problem in the operation, and the two-component urethane resin composition for the honing pad excellent in various honing properties is And the development of a polyurethane lining pad made of it is highly desirable.
[專利文獻1]特開2005-68168號公報[Patent Document 1] JP-A-2005-68168
本發明之目的為提供一種成形作業時之反應性的控制為容易且可均勻地形成微細形狀之發泡胞(胞控制性)，且耐久性(耐熱水性)、耐摩耗性、成形性(產率、成形不均等)優良的硏磨墊用2液型胺基甲酸酯樹脂組成物。An object of the present invention is to provide a foaming cell (cell controllability) which is easy to control and can form a fine shape in a molding operation, and has durability (heat resistant water), abrasion resistance, and formability. The honing pad excellent in rate, uneven formation, etc. is a two-component urethane resin composition.
又提供一種高硬度聚胺基甲酸酯硏磨墊，其係使用適合於將半導體基板、光學基板、磁性基板等之要求高度表面平坦性的玻璃材料予以平坦化之該硏磨墊用2液型胺基甲酸酯樹脂組成物而成、及聚胺基甲酸酯硏磨墊之製法。Further, a high-hardness polyurethane lining pad is provided which uses a liquid material suitable for flattening a glass material which requires a high surface flatness such as a semiconductor substrate, an optical substrate, or a magnetic substrate. A method for preparing a urethane resin composition and a polyurethane lining pad.
本發明人欲解決上記課題而進行鑽硏探討，結果發現：在由含有異氰酸酯基末端胺基甲酸酯預聚物之主劑、與含有異氰酸酯基反應性化合物、作為發泡劑之水及觸媒之硬化劑所構成的硏磨墊用2液型胺基甲酸酯樹脂組成物中，前述預聚物係使作為聚異氰酸酯之聯甲苯胺二異氰酸酯與二醇反應而得之異氰酸酯基末端胺基甲酸酯預聚物，藉由限定前述預聚物合成時，異氰酸酯基與羥基的莫耳比(即「NCO/OH莫耳比」)、前述胺基甲酸酯預聚物之NCO當量、前述莫耳比與NCO當量的積於特定之範圍內，可得到耐久性(耐熱水性)、耐摩耗性、成形性(例如，產率、成形不均)優良，且作業時之反應性控制為容易，能形成均勻且微細形狀之胞的硏磨墊用2液型胺基甲酸酯樹脂組成物、使用它而成之高硬度聚胺基甲酸酯硏磨墊、及聚胺基甲酸酯硏磨墊之製法，而完成了本發明。The inventors of the present invention conducted a drill collar investigation to solve the above problems, and found that the main component containing an isocyanate-terminated urethane prepolymer, and a compound containing an isocyanate-based reactive compound and a foaming agent are touched. A two-component urethane resin composition for a honing pad comprising a curing agent for a medium, wherein the prepolymer is an isocyanate-terminated amine obtained by reacting a toluidine diisocyanate as a polyisocyanate with a diol. a urethane prepolymer which, by defining the prepolymer, synthesizes the molar ratio of isocyanate groups to hydroxyl groups (i.e., "NCO/OH molar ratio"), NCO equivalent of the aforementioned urethane prepolymer When the product of the molar ratio and the NCO equivalent is within a specific range, durability (hot water resistance), abrasion resistance, formability (for example, yield, unevenness in formation) are excellent, and reactivity control during operation is obtained. A two-component urethane resin composition which is easy to form a uniform and fine-shaped cell, a high-hardness polyurethane lining pad which is formed using the same, and a polyamine group The invention has been prepared by the method of preparing an acid ester pad
亦即，本發明係提供一種硏磨墊用2液型胺基甲酸酯樹脂組成物，特徵為其係以含有異氰酸酯基末端胺基甲酸酯預聚物(A)之主劑與包括具有含活性氫的基之化合物(b1)的硬化劑(B)為必須成分之硏磨墊用胺基甲酸酯樹脂組成物，前述預聚物(A)係使聯甲苯胺二異氰酸酯(a1)與二醇(a2)反應而得者，在其合成時，前述聯甲苯胺二異氰酸酯(a1)之異氰酸酯基與前述二醇(a2)羥基的莫耳比(α)為2.10~2.30，前述預聚物(A)之NCO當量(β)為460~550，且前述莫耳比(α)與NCO當量(β)的積(α×β)為1055~1265之範圍。That is, the present invention provides a two-component urethane resin composition for an honing pad, characterized by comprising a main component containing an isocyanate-terminated urethane prepolymer (A) and comprising The hardener (B) of the active hydrogen-containing compound (b1) is an essential component of a urethane resin composition for a honing pad, and the prepolymer (A) is a tolidine diisocyanate (a1). In the synthesis of the diol (a2), the molar ratio (α) of the isocyanate group of the tolidine diisocyanate (a1) to the hydroxy group of the diol (a2) is 2.10 to 2.30. The NCO equivalent (β) of the polymer (A) is 460 to 550, and the product (α × β) of the molar ratio (α) and the NCO equivalent (β) is in the range of 1055 to 1265.
又，本發明亦提供一種使用前述硏磨墊用異氰酸酯基末端胺基甲酸酯預聚物而成之聚胺基甲酸酯硏磨墊。Further, the present invention also provides a polyurethane lining pad which is obtained by using the isocyanate-based terminal urethane prepolymer of the aforementioned honing pad.
又，本發明亦提供一種聚胺基甲酸酯硏磨墊之製法，其特徵係將前述硏磨墊用2液型胺基甲酸酯樹脂組成物注入鑄模內使其發泡、硬化，將該發泡成形物從鑄模取出，並切片成片狀。Moreover, the present invention also provides a method for producing a polyurethane lining pad, characterized in that the honing pad is injected into a mold with a two-component urethane resin composition to be foamed and hardened. The foamed molded article was taken out from the mold and sliced into a sheet shape.
本發明之硏磨墊用2液型胺基甲酸酯樹脂組成物可使作業時之反應性控制為容易，成形性優良，能容易形成均勻且微細形狀之發泡胞。The two-component urethane resin composition for the honing pad of the present invention can easily control the reactivity at the time of work, and is excellent in moldability, and can easily form a uniform and fine-shaped foamed cell.
又，本發明之聚胺基甲酸酯硏磨墊係因硏磨操作時之溫度上昇導致硏磨墊的硬度(彈性模數)改變小、耐久性(耐熱水性等)、耐摩耗性、成形性(產率、成形不均等)優良，可用於例如，液晶顯示器(LCD)用玻璃基板、硬碟(HDD)用玻璃基板、記錄裝置用玻璃碟片、光學用透鏡、矽晶圓、半導體元件等之半導體基板、光學基板、磁性基板等要求高度表面平坦性之玻璃材料的精密硏磨。Further, the polyurethane lining pad of the present invention has a small change in hardness (elastic modulus) of the honing pad due to an increase in temperature during the honing operation, durability (heat-resistant water resistance, etc.), abrasion resistance, and formation. It is excellent in properties (yield, uneven molding, etc.) and can be used, for example, in a glass substrate for a liquid crystal display (LCD), a glass substrate for a hard disk (HDD), a glass disk for a recording device, an optical lens, a germanium wafer, and a semiconductor element. Precision honing of glass materials requiring high surface flatness such as semiconductor substrates, optical substrates, and magnetic substrates.
首先，針對本發明之硏磨墊用2液型胺基甲酸酯樹脂組成物加以說明。First, the two-component urethane resin composition for the honing pad of the present invention will be described.
前述硏磨墊用2液型胺基甲酸酯樹脂組成物係將含有異氰酸酯基末端胺基甲酸酯預聚物(A)之主劑與含有異氰酸酯基反應性化合物(b1)之硬化劑(B)調配、混合而成。The two-component urethane resin composition for the honing pad is a main component containing an isocyanate group-terminated urethane prepolymer (A) and a hardener containing an isocyanate-reactive compound (b1) ( B) Blending and mixing.
前述異氰酸酯基末端胺基甲酸酯預聚物(A)(以下簡稱「預聚物(A)」)可使作為聚異氰酸酯之聯甲苯胺二異氰酸酯(a1)與二醇反應而得。The isocyanate group-terminated urethane prepolymer (A) (hereinafter referred to as "prepolymer (A)") can be obtained by reacting a toluidine diisocyanate (a1) as a polyisocyanate with a diol.
在本發明，於前述預聚物(A)之合成時，藉由單獨使用聯甲苯胺二異氰酸酯(a1)作為聚異氰酸酯，而聯甲苯胺二異氰酸酯之分子構造係富有對稱性，因此可得聚胺基甲酸酯樹脂中之硬鏈段構造的高結晶化(高凝集)所致之高硬度化、耐久性(耐熱水性)、耐摩耗性等優良特性。In the present invention, in the synthesis of the prepolymer (A), by using tolidine diisocyanate (a1) as a polyisocyanate alone, and the molecular structure of the tolidine diisocyanate is symmetrical, it is possible to obtain a poly In the urethane resin, the hard segment structure has excellent properties such as high hardness (high agglomeration), high hardness, durability (hot water resistance), and abrasion resistance.
前述聯甲苯胺二異氰酸酯(a1)係存在異構物，此等之中，o-聯甲苯胺二異氰酸酯(別名；3,3’-二甲基-4,4’-聯苯二異氰酸酯)由於可使聚胺基甲酸酯樹脂中硬鏈段構造之高結晶化(高凝集化)所致之硏磨性更佳提升，因而特佳。The above-mentioned tolidine diisocyanate (a1) is an isomer, among which o-tolidine diisocyanate (alias; 3,3'-dimethyl-4,4'-biphenyl diisocyanate) due to It is particularly preferable that the honing property due to high crystallization (high agglomeration) of the hard segment structure in the polyurethane resin can be improved.
再者，在本發明預聚物(A)之合成時，雖係單獨使用聯甲苯胺二異氰酸酯(a1)，但在不阻害本發明目的之範圍內，亦可使用其他聚異氰酸酯。Further, in the synthesis of the prepolymer (A) of the present invention, tolylene diisocyanate (a1) is used alone, other polyisocyanates may be used within a range not inhibiting the object of the present invention.
作為前述其他聚異氰酸酯，可舉出例如，二苯基甲烷二異氰酸酯(略稱MDI；其4,4’-體、2,4’-體、或2,2’-體、或是此等之混合物)、聚亞甲基聚苯基聚異氰酸酯、碳二醯亞胺化二苯基甲烷聚異氰酸酯、甲苯二異氰酸酯(TDI；其2,4-體、或2,6-體、或是此等之混合物)、二甲苯二異氰酸酯(XDI)、1,5-萘二異氰酸酯(NDI)、四甲基二甲苯二異氰酸酯等之芳香族系二異氰酸酯、或異佛爾酮二異氰酸酯(IPDI)、加氫二苯基甲烷二異氰酸酯(加氫MDI)、加氫二甲苯二異氰酸酯(加氫XDI)等之脂環族系二異氰酸酯、或六亞甲基二異氰酸酯、二聚物酸二異氰酸酯、降莰烯二異氰酸酯等之脂肪族系二異氰酸酯等，在不損害本發明之目的的範圍內，亦可使用此等中之一種或二種以上。Examples of the other polyisocyanate include diphenylmethane diisocyanate (abbreviated as MDI; 4,4′-form, 2,4′-form, or 2,2′-form, or the like). Mixture), polymethylene polyphenyl polyisocyanate, carbodiimidated diphenylmethane polyisocyanate, toluene diisocyanate (TDI; 2,4-body, or 2,6-body, or such Mixture), an aromatic diisocyanate such as xylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI) or tetramethylxylene diisocyanate, or isophorone diisocyanate (IPDI), plus An alicyclic diisocyanate such as hydrogen diphenylmethane diisocyanate (hydrogenated MDI) or hydrogenated xylene diisocyanate (hydrogenated XDI), or hexamethylene diisocyanate, dimer acid diisocyanate, orthoquinone An aliphatic diisocyanate such as an ene diisocyanate or the like may be used alone or in combination of two or more kinds within the range not impairing the object of the present invention.
作為前述其他聚異氰酸酯，例如，當二苯基甲烷二異氰酸酯(MDI)的使用量增加時，所得聚胺基甲酸酯樹脂中硬鏈段構造的結晶化降低，而有難以得到高硬度化、耐久性(耐熱水性)、耐摩耗性所致之硏磨性提升的傾向，而不佳。因此，其他聚異氰酸酯的使用量宜考慮與所期望之特性的平衡來加以設定As the other polyisocyanate, for example, when the amount of use of diphenylmethane diisocyanate (MDI) is increased, the crystallization of the hard segment structure in the obtained polyurethane resin is lowered, and it is difficult to obtain high hardness. The tendency of durability (heat-resistant water resistance) and abrasion resistance due to abrasion resistance is not good. Therefore, the amount of other polyisocyanates should be set in consideration of the balance with the desired characteristics.
前述預聚物(A)係將聯甲苯胺二異氰酸酯(a1)與二醇依照通常方法使其反應而得，前述二醇可使用單一的二醇、或亦可組合特定數平均分子量(以下簡稱為「Mn」)的高分子量二醇(a2)及特定分子量的低分子量二醇(a22)之至少2種二醇使其反應，併用高分子量二醇(a21)及低分子量二醇(a22)，將本發明之胺基甲酸酯樹脂組成物予以發泡、硬化成形時，能夠更有效地控制反應性，可容易控制作業時之反應性，成形性(產率、成形不均等)優良，且可形成均勻且微細形狀之發泡胞，因而更佳。The prepolymer (A) is obtained by reacting tolidine diisocyanate (a1) and a diol according to a usual method, and the diol may be a single diol or may be combined with a specific number average molecular weight (hereinafter referred to as a short name). A high molecular weight diol (a2) of "Mn") and at least two kinds of diols of a low molecular weight diol (a22) having a specific molecular weight are reacted, and a high molecular weight diol (a21) and a low molecular weight diol (a22) are used. When the urethane resin composition of the present invention is foamed and hardened, the reactivity can be more effectively controlled, the reactivity at the time of work can be easily controlled, and the moldability (yield, molding unevenness, etc.) is excellent. Further, a foamed cell having a uniform and fine shape can be formed, and thus is more preferable.
前述高分子量二醇(a21)之Mn較佳為500~5000之範圍，更佳為500~2000之範圍。The Mn of the high molecular weight diol (a21) is preferably in the range of 500 to 5,000, more preferably in the range of 500 to 2,000.
作為前述高分子量二醇(a21)，可舉出例如，聚乙二醇(PEG)、聚丙二醇(PPG)、聚伸乙基丙二醇(PEPG)、聚四亞甲基乙二醇(PTMG)、2-甲基-1,3-丙烷己二酸、3-甲基-1,5戊烷己二酸、聚碳酸酯聚醇等，此等之中，較佳為Mn為500~2000之聚四亞甲基乙二醇(PTMG)。前述高分子量二醇(a21)可為直鏈、分枝、環狀構造之任一者。Examples of the high molecular weight diol (a21) include polyethylene glycol (PEG), polypropylene glycol (PPG), polyethyl propylene glycol (PEPG), and polytetramethylene glycol (PTMG). 2-methyl-1,3-propane adipic acid, 3-methyl-1,5-pentane adipic acid, polycarbonate polyalcohol, etc., among which Mn is preferably 500 to 2000. Tetraethylene glycol (PTMG). The high molecular weight diol (a21) may be any of a linear, branched or cyclic structure.
又，前述低分子量二醇(a22)之分子量較佳為50~300之範圍，更佳為分子量為50~200之範圍。Further, the molecular weight of the low molecular weight diol (a22) is preferably in the range of 50 to 300, and more preferably in the range of 50 to 200.
作為前述低分子量二醇(a22)，可舉出例如，乙二醇(EG)、丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、二乙二醇(DEG)、三乙二醇、四乙二醇、二丙二醇、三丙二醇、3-甲基-1,5-戊二醇、2-丁基-2-乙基1,3-丙二醇、2-甲基-1,3-丙二醇等之脂肪族二醇、1,4-環己二醇、1,4-環己烷二甲醇、加氫雙酚A等之脂環族二醇等，作為3官能以上之成分，可舉出甘油、三羥甲基丙烷、新戊四醇等，此等之中，較佳為二乙二醇(DEG)。前述低分子量二醇(a22)可為直鏈、分枝、環狀構造之任一者。The low molecular weight diol (a22) may, for example, be ethylene glycol (EG), propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1,5- Pentylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5- An aliphatic diol such as pentanediol, 2-butyl-2-ethyl1,3-propanediol or 2-methyl-1,3-propanediol, 1,4-cyclohexanediol, 1,4-ring Examples of the alicyclic diol such as hexane dimethanol or hydrogenated bisphenol A include glycerin, trimethylolpropane, and pentaerythritol, and among them, preferred. It is diethylene glycol (DEG). The low molecular weight diol (a22) may be any of a linear, branched or cyclic structure.
在本發明，較佳為組合前述高分子量二醇(a21)與低分子量二醇(a22)使其反應，此等之中，以高分子量二醇(a21)係聚伸丁二醇(PTMG，特佳為Mn為500~2000)及低分子量二醇(a22)係二乙二醇(DEG)之組合為特佳，藉此能夠使作業時之反應性的控制更為容易，成形性(產率、成形不均等)優良，可形成均勻且微細形狀之發泡胞。In the present invention, it is preferred to combine the high molecular weight diol (a21) and the low molecular weight diol (a22) to react, among which high molecular weight diol (a21) is used to polymerize butanediol (PTMG, Particularly preferred is a combination of Mn of 500 to 2,000 and a low molecular weight diol (a22)-based diethylene glycol (DEG), whereby the control of reactivity during work can be more easily controlled. The rate, uneven shape, etc. are excellent, and a foamed cell having a uniform and fine shape can be formed.
前述預聚物(A)係在使作為聚異氰酸酯之聯甲苯胺二異氰酸酯(a1)與二醇(較佳為Mn為特定範圍的高分子量二醇(a21)及分子量為特定之範圍的低分子量二醇(a22))反應而成的分子末端具有異氰酸酯基之預聚物，全部滿足下述[條件I]、[條件II]、[條件III]者。The prepolymer (A) is a low molecular weight of a polyisocyanate diisocyanate (a1) as a polyisocyanate and a diol (preferably Mn is a specific range of high molecular weight diol (a21) and a molecular weight of a specific range). The prepolymer having an isocyanate group at the molecular terminal of the reaction of the diol (a22)) satisfies all of the following [Condition I], [Condition II], and [Condition III].
[條件I]預聚物(A)合成時之異氰酸酯基與羥基的莫耳比(α)(即NCO/OH莫耳比)係2.10~2.30之範圍。[Condition I] The molar ratio (α) (i.e., NCO/OH molar ratio) of the isocyanate group to the hydroxyl group in the synthesis of the prepolymer (A) is in the range of 2.10 to 2.30.
[條件II]預聚物(A)之NCO當量(β)為460~550之範圍。[Condition II] The NCO equivalent (β) of the prepolymer (A) is in the range of 460 to 550.
[條件III]莫耳比(α)與NCO當量(β)的積(α×β)為1055~1265之範圍。[Condition III] The product (α × β) of the molar ratio (α) and the NCO equivalent (β) is in the range of 1055 to 1265.
若前述預聚物(A)之莫耳比(α)、NCO當量(β)、積(α×β)完全滿足[條件I]~[要件III]，則成形性、耐磨耗性、耐久性優良，且作業時之反應性控制為容易，可形成均勻且微細形狀之發泡胞。If the molar ratio (α), NCO equivalent (β), and product (α×β) of the prepolymer (A) completely satisfy [Condition I] to [Requirement III], formability, wear resistance, and durability The property is excellent, and the reactivity at the time of operation is controlled to be easy, and a foamed cell having a uniform and fine shape can be formed.
再者，在本發明中，當量的單位係使用「g/eq」。Further, in the present invention, the unit of the equivalent is "g/eq".
構成主劑之預聚物(A)具有下述2個特徵，因此藉由與後述硬化劑組合、調配、混合，可發揮優異的性能。Since the prepolymer (A) constituting the main component has the following two characteristics, it can exhibit excellent performance by being combined, blended, and mixed with a curing agent to be described later.
[預聚物(A)之特徵1]單獨使用聯甲苯胺二異氰酸酯(TODI)。[Feature 1 of Prepolymer (A)] Tolidine diisocyanate (TODI) was used alone.
習知的硏磨墊用2液型胺基甲酸酯樹脂組成物之主流係以甲苯二異氰酸酯(TDI)等作為主要之聚異氰酸酯成分，惟與此等相較，本發明的特徵係在主劑之預聚物(A)的必要反應原料中不使用TDI等作為聚異氰酸酯，而單獨使用TODI。TODI比TDI更具有分子構造之對稱性，因此可有效賦予所得聚胺基甲酸酯樹脂中硬鏈段構造之高結晶化(高凝集化)所致的高硬度化、耐久性(特別是耐熱水性)、耐摩耗性。In the conventional honing pad, the main component of the two-component urethane resin composition is toluene diisocyanate (TDI) or the like as a main polyisocyanate component, but the characteristics of the present invention are mainly in comparison with the above. In the necessary reaction raw material of the prepolymer (A), TDI or the like is not used as the polyisocyanate, and TODI is used alone. Since TODI has more molecular structure symmetry than TDI, it can effectively impart high hardness and durability (especially heat resistance) due to high crystallization (high agglomeration) of the hard segment structure in the obtained polyurethane resin. Water-based), abrasion resistance.
[預聚物(A)之特徵2]併用高分子量二醇(a21)與低分子量二醇(a22)以將TODI之反應性調整為最適範圍。[Feature 2 of Prepolymer (A)] A high molecular weight diol (a21) and a low molecular weight diol (a22) were used in combination to adjust the reactivity of TODI to an optimum range.
聚異氰酸酯之反應性係TODI比TDI快，TODI具有反應難以控制、發泡成形性差等缺點。因此，本發明為了盡可能減低反應後之無異氰酸酯殘存量，在使TODI單獨與二醇反應合成預聚物(A)之際，較佳為併用高分子量二醇(a21)與低分子量二醇(a22)，藉由分別將預聚物(A)在合成時之異氰酸酯基與羥基的莫耳比(α)(亦即，NCO/OH莫耳比)2.10~2.30之範圍、前述預聚物(A)之NCO當量(β)設定於460~550之範圍、且前述莫耳比(α)與前述NCO當量(β)的積(α×β)設定於1055~1265之範圍，將TODI的反應性調整為最適範圍，以謀求發泡成形性之適當化。The reactivity of polyisocyanate is faster than TDI, and TODI has disadvantages such as difficulty in control of reaction and poor foam formability. Therefore, in order to minimize the residual amount of isocyanate after the reaction, in order to react the TODI alone with the diol to synthesize the prepolymer (A), it is preferred to use a high molecular weight diol (a21) and a low molecular weight diol in combination. (a22), the prepolymer by the molar ratio (α) of the isocyanate group to the hydroxyl group (i.e., NCO/OH molar ratio) in the range of 2.10 to 2.30, respectively, of the prepolymer (A) The NCO equivalent (β) of (A) is set in the range of 460 to 550, and the product (α×β) of the molar ratio (α) and the NCO equivalent (β) is set in the range of 1055 to 1265, and the TODI is The reactivity is adjusted to an optimum range, and the foam formability is optimized.
接著，以下說明與前述主劑組合、調配、混合之硬化劑。Next, a curing agent which is combined, blended, and mixed with the above-mentioned main agent will be described below.
本發明所用之硬化劑(B)係含有異氰酸酯基反應性化合物(b1)(以下簡稱為「反應性化合物(b1)」)作為必須成分。The curing agent (B) used in the present invention contains an isocyanate group-reactive compound (b1) (hereinafter simply referred to as "reactive compound (b1)") as an essential component.
又，以後述水發泡法製造硏磨墊時，硏磨墊用2液型胺基甲酸酯樹脂組成物的硬化劑(B)中含有作為發泡劑之水(C)與觸媒(D)作為必須成分。Further, when the honing pad is produced by the water foaming method described later, the hardener (B) of the two-component urethane resin composition for the honing pad contains water (C) and a catalyst as a foaming agent ( D) as an essential component.
只要前述反應性化合物(b1)對具有異氰酸酯基之化合物具有良好的反應性，則無特別限定，可舉出例如，聚胺基氯苯基甲烷化合物、Pandex E-50(商品名，DIC股份有限公司製，聚胺基氯苯基甲烷化合物)、聚胺基氯苯基甲烷化合物之二核體的4,4’-二胺基-3,3’-二氯二苯基甲烷(以下稱為MOCA)與聚伸丁二醇(以下稱為PTMG)之混合物等，此等係可單獨使用，亦可併用2種以上。The reactive compound (b1) is not particularly limited as long as it has good reactivity with a compound having an isocyanate group, and examples thereof include a polyaminochlorophenylmethane compound and a Pandex E-50 (trade name, DIC stock limited). 4,4'-diamino-3,3'-dichlorodiphenylmethane (hereinafter referred to as "polyaminochlorophenylmethane compound"), dinuclear of polyaminochlorophenylmethane compound (hereinafter referred to as A mixture of MOCA) and polybutanediol (hereinafter referred to as PTMG) may be used singly or in combination of two or more.
前述反應性化合物(b1)之調配量相對於前述預聚物(A)100重量份而言，較佳為15~35重量份之範圍，更佳為20~32重量份之範圍。若前述反應性化合物(B)之調配量在此範圍內，則可得高硬度且耐久性(耐熱水性)、耐摩耗性優異的聚胺基甲酸酯硏磨墊。The amount of the reactive compound (b1) to be added is preferably from 15 to 35 parts by weight, more preferably from 20 to 32 parts by weight, per 100 parts by weight of the prepolymer (A). When the compounding amount of the reactive compound (B) is within this range, a polyurethane lining pad having high hardness, durability (heat resistant water), and abrasion resistance can be obtained.
又，水(C)係擔任發泡劑之作用而調配。水之調配量相對於前述反應性化合物(b1)100重量份而言，較佳為0.05~1重量份之範圍，更佳為0.30~0.60重量份之範圍。若前述水(C)之調配量在此範圍內，則可得具有安定發泡狀態之硏磨墊。Further, water (C) is formulated as a foaming agent. The amount of water to be added is preferably in the range of 0.05 to 1 part by weight, more preferably 0.30 to 0.60 part by weight, per 100 parts by weight of the reactive compound (b1). If the amount of the water (C) is within this range, a honing pad having a stable foaming state can be obtained.
將主劑與硬化劑予以2液混合時水(C)之添加方法並無特別限定，可舉出例如，預先將反應性化合物(B)、水(C)、觸媒(D)與視需要的添加劑混合作為硬化劑，接著，使主劑與硬化劑混合、發泡、硬化之方法等。The method of adding the water (C) when the main agent and the curing agent are mixed in two liquids is not particularly limited, and for example, the reactive compound (B), water (C), and catalyst (D) are optionally used in advance, as needed. The additive is mixed as a hardener, followed by a method of mixing the main agent with the hardener, foaming, hardening, and the like.
進一步地，本發明之硏磨墊用2液型胺基甲酸酯樹脂組成物必須含有觸媒(D)。Further, the two-component urethane resin composition for the honing pad of the present invention must contain a catalyst (D).
前述觸媒(D)之種類及添加量只要是考慮混合步驟後流入規定形狀之鑄模內的時間、最終發泡狀態等來加以選擇即可，沒有特別限定。The type and the amount of the above-mentioned catalyst (D) are not particularly limited as long as they are selected in consideration of the time of flowing into the mold of a predetermined shape after the mixing step, the final foaming state, and the like.
作為前述觸媒(D)，可舉出例如，N,N-二甲基胺基乙基醚、TOYOCAT ET(商品名，東曹股份有限公司製，N,N-二甲基胺基乙基醚)、三伸乙二胺、二甲基乙醇胺、三乙醇胺、N,N,N’,N’-四甲基六亞甲基二胺、N-甲基咪唑等之三級胺、二辛錫二月桂酸酯等之金屬系觸媒等，此等之中，由泡化特性為強的點來看，較佳為N,N-二甲基胺基乙基醚、TOYOCAT ET，此等係可單獨使用，亦可併用2種以上。Examples of the catalyst (D) include N,N-dimethylaminoethyl ether and TOYOCAT ET (trade name, manufactured by Tosoh Corporation, N,N-dimethylaminoethyl). Ether), triethylenediamine, dimethylethanolamine, triethanolamine, N,N,N',N'-tetramethylhexamethylenediamine, N-methylimidazole, etc. Among the metal-based catalysts such as tin dilaurate, etc., among these, from the viewpoint that the foaming property is strong, N,N-dimethylaminoethyl ether and TOYOCAT ET are preferable. They may be used singly or in combination of two or more.
前述觸媒(D)之調配量相對於異氰酸酯基反應性化合物(B)100重量份而言，較佳為0.1~1重量份之範圍，更佳為0.3~0.6重量份之範圍。若前述觸媒(D)之調配量在此範圍內，可得具有安定發泡狀態之硏磨墊。The amount of the catalyst (D) to be added is preferably in the range of 0.1 to 1 part by weight, more preferably 0.3 to 0.6 part by weight, per 100 parts by weight of the isocyanate group-reactive compound (B). If the amount of the above-mentioned catalyst (D) is within this range, a honing pad having a stable foaming state can be obtained.
以前述調配量之範圍調配作為必須成分之反應性化合物(B)、水(C)、觸媒(D)，藉由充分地攪拌混合可得硬化劑。The reactive compound (B), water (C), and catalyst (D), which are essential components, are blended in the range of the above-mentioned blending amount, and a hardener is obtained by sufficiently stirring and mixing.
如上所述調配經調整的主劑與硬化劑，直接充分地攪拌混合，可得本發明之硏磨墊用2液型胺基甲酸酯樹脂組成物。The adjusted main agent and the hardener are blended as described above, and the mixture is directly stirred and mixed sufficiently to obtain a two-component urethane resin composition for a honing pad of the present invention.
前述主劑與硬化劑之調配比，亦即，[主劑中之異氰酸酯基之總莫耳數]/[含水之硬化劑中之異氰酸酯基反應性基之合計莫耳數]較佳為1/0.7~1/1.1之範圍，更佳為1/0.8~1/1.0之範圍。若主劑與硬化劑的調配比在此範圍內，則可得高硬度，耐久性(耐熱水性)、耐摩耗性等優異特性。The ratio of the ratio of the main agent to the hardener, that is, [the total number of moles of the isocyanate group in the main agent] / [the total number of moles of the isocyanate-reactive group in the aqueous hardener] is preferably 1/ The range of 0.7 to 1/1.1 is more preferably in the range of 1/0.8 to 1/1.0. When the blending ratio of the main component and the curing agent is within this range, excellent properties such as high hardness, durability (heat resistant water), and abrasion resistance can be obtained.
在本發明之硏磨墊用2液型胺基甲酸酯樹脂組成物中，在不損及本發明目的之範圍內，亦可在製造步驟的任何階段使用例如整泡劑、抗氧化劑、脫泡劑、紫外線吸收劑、硏磨粒、填充劑、顏料、增黏劑、界面活性劑、難燃劑、可塑劑、滑劑、防靜電劑、耐熱安定劑、摻合用樹脂等作為添加劑。In the two-component urethane resin composition for the honing pad of the present invention, for example, a foam stabilizer, an antioxidant, or a detachment may be used at any stage of the production step without damaging the object of the present invention. A foaming agent, a UV absorber, a honing agent, a filler, a pigment, a tackifier, a surfactant, a flame retardant, a plasticizer, a slip agent, an antistatic agent, a heat stabilizer, a blending resin, or the like is used as an additive.
作為前述填充材，沒有特別限定，可舉出例如，碳酸鹽、矽酸、矽酸鹽、氫氧化物、硫酸鹽、硼酸鹽、鈦酸鹽、金屬氧化物、碳化物、有機物等。The filler is not particularly limited, and examples thereof include a carbonate, a citric acid, a citrate, a hydroxide, a sulfate, a borate, a titanate, a metal oxide, a carbide, and an organic substance.
作為前述整泡劑，可舉出Toray Silicone SH-193(東麗道康寧股份有限公司製)、SH-192(同公司製)、SH-190(同公司製)等。Examples of the foam stabilizer include Toray Silicone SH-193 (manufactured by Toray Industries, Inc.), SH-192 (manufactured by Toray Industries, Inc.), and SH-190 (manufactured by Kyoto Co., Ltd.).
接著針對本發明之聚胺基甲酸酯硏磨墊及其製法加以說明。Next, the polyurethane lining pad of the present invention and a method for producing the same will be described.
本發明之聚胺基甲酸酯硏磨墊係使用前述硏磨墊用2液型胺基甲酸酯樹脂組成物而成者，可在前述硏磨墊用2液型胺基甲酸酯樹脂組成物中視需要加入添加劑，注入預定形狀的鑄模內使發泡、硬化，將該發泡成形物從鑄模取出，切片成片狀等之適當形狀等加工而得。The polyurethane lining pad of the present invention is a two-component urethane resin composition for the honing pad, and a two-component urethane resin for the honing pad. The composition is added to the composition as needed, and is injected into a mold having a predetermined shape to be foamed and hardened, and the foamed product is taken out from the mold, and sliced into a sheet shape or the like to obtain a suitable shape.
作為本發明之聚胺基甲酸酯硏磨墊之製法，除了後述水發泡法以外，亦可採用例如，添加中空珠粒之方法、機械發泡法、化學發泡法等各種方法，沒有特別限制。As a method for producing the polyurethane lining pad of the present invention, in addition to the water foaming method described later, various methods such as a method of adding hollow beads, a mechanical foaming method, and a chemical foaming method may be employed. Special restrictions.
以下，舉水發泡法作為例子，說明本發明之製法。Hereinafter, the water-foaming method will be described as an example to explain the production method of the present invention.
使用前述硏磨墊用2液型胺基甲酸酯樹脂組成物的聚胺基甲酸酯硏磨墊之製法，可例示例如，包括如下[步驟1]~[步驟5]的一連串之製法，惟不限於此。The method for producing the polyurethane lining pad using the two-component urethane resin composition for the honing pad can be exemplified by a series of methods including the following [Step 1] to [Step 5], It is not limited to this.
再者，添加劑只要可無阻礙地添加且能夠均勻調配，則可在任何步驟使用。Further, the additive can be used in any step as long as it can be added unimpeded and can be uniformly formulated.
在具備氮導入管、冷卻冷凝器、溫度計、冷卻機之反應裝置中，分別裝入作為聚異氰酸酯之聯甲苯胺二異氰酸酯(a1)、高分子量二醇(a21)(Mn為500~5000之範圍)、低分子量二醇(a22)(分子量為50~300)，使得預聚物(A)在合成時之異氰酸酯基與羥基的莫耳比(α)為2.10~2.30之範圍，前述預聚物(A)之NCO當量(β)為460~550之範圍，且前述莫耳比(α)與前述NCO當量(β)的積(α×β)為1055~1265之範圍，在氮氛圍氣下邊攪拌邊在較佳為50~90℃之範圍、更佳為60~80℃之範圍使其反應，合成預聚物(A)而得含有預聚物(A)之主劑。In a reaction apparatus equipped with a nitrogen introduction tube, a cooling condenser, a thermometer, and a cooling device, toluidine diisocyanate (a1) and a high molecular weight diol (a21) as polyisocyanate are respectively charged (the range of Mn is 500 to 5,000) a low molecular weight diol (a22) (having a molecular weight of 50 to 300) such that the prepolymer (A) has a molar ratio (α) of isocyanate groups to hydroxyl groups in the range of 2.10 to 2.30, and the prepolymer The NCO equivalent (β) of (A) is in the range of 460 to 550, and the product (α×β) of the aforementioned molar ratio (α) and the aforementioned NCO equivalent (β) is in the range of 1055 to 1265, and is under a nitrogen atmosphere. The prepolymer (A) is synthesized by stirring in a range of preferably from 50 to 90 ° C, more preferably from 60 to 80 ° C to obtain a prepolymer (A).
接著，將含有前述預聚物(A)之主劑與至少含有反應性化合物(B)、水(C)、及觸媒(D)之硬化劑予以混合、攪拌做成發泡反應液。於混合之際，將預聚物(A)與含有水(C)及觸媒(D)之反應性化合物(B)分別置入二液混合澆鑄機的各自槽中，將含有前述預聚物(A)之主劑加溫至較佳為40~70℃，硬化劑較佳為加溫至40~90℃，各自以二液混合澆鑄機進行混合。Next, the main component containing the prepolymer (A) and a curing agent containing at least the reactive compound (B), water (C), and catalyst (D) are mixed and stirred to prepare a foaming reaction liquid. At the time of mixing, the prepolymer (A) and the reactive compound (B) containing water (C) and catalyst (D) are separately placed in respective tanks of a two-liquid mixing casting machine, and the prepolymer is contained. The main agent of (A) is preferably heated to 40 to 70 ° C, and the hardener is preferably heated to 40 to 90 ° C, and each is mixed by a two-liquid mixing casting machine.
將前述發泡反應液注入預先加溫至較佳為50~120℃的鑄模內。The foaming reaction liquid is injected into a mold which is previously heated to preferably 50 to 120 °C.
以注入鑄模內之狀態，將發泡反應液加熱保持在適合的溫度範圍(例如，50~120℃之範圍)，使其發泡、硬化，較佳為在50~120℃之模具內放置30分鐘~2小時後，取出該成形品，以較佳為100~120℃、8~17小時的條件進行後硬化(after cure)，做為成形品。The foaming reaction solution is heated and maintained in a suitable temperature range (for example, in the range of 50 to 120 ° C) in a state of being injected into the mold to be foamed and hardened, preferably placed in a mold of 50 to 120 ° C. After the minute to 2 hours, the molded article is taken out and post-cured at a temperature of preferably 100 to 120 ° C for 8 to 17 hours to form a molded article.
將前述成形品切片為適合的厚度之片狀。切片後之片厚只要依照硏磨目的加以設定即可，無特別限制，例如較佳為0.6~2.0mm之範圍。The molded article is sliced into a sheet having a suitable thickness. The sheet thickness after slicing is not particularly limited as long as it is set in accordance with the purpose of honing, and is preferably in the range of, for example, 0.6 to 2.0 mm.
如上所述，本發明之聚胺基甲酸酯硏磨墊係硏磨操作時因溫度上昇導致之硏磨墊硬度(彈性模數)改變為小、耐久性(耐熱水性等)、耐摩耗性、成形性(產率、成形不均等)優異，可用於例如，液晶顯示器(LCD)用玻璃基板、硬碟(HDD)用玻璃基板、顯示器用玻璃基板、記錄裝置用玻璃碟片、光學用透鏡、矽晶圓、半導體元件等之要求高度表面平坦性的玻璃材料之精密硏磨。As described above, the polyurethane lining pad of the present invention has a small change in the hardness (elastic modulus) of the honing pad due to an increase in temperature during the honing operation, and wear resistance. It is excellent in moldability (yield, molding unevenness, etc.), and can be used for, for example, a glass substrate for a liquid crystal display (LCD), a glass substrate for a hard disk (HDD), a glass substrate for a display, a glass disk for a recording device, and an optical lens. Precision honing of glass materials requiring high surface flatness, such as wafers and semiconductor components.
以下藉由實施例進一步具體說明本發明，惟本發明之範圍係不僅限於此等實施例。The invention is further illustrated by the following examples, but the scope of the invention is not limited to the examples.
又，在本發明，若無特別限定，「份」為「重量份」，「%」為「重量%」。Further, in the present invention, unless otherwise specified, "parts" are "parts by weight" and "%" is "% by weight".
再者，本發明所用之測定方法及評價方法係如以下所示。Further, the measurement method and evaluation method used in the present invention are as follows.
又，本發明中藉由GPC之重量平均分子量(聚苯乙烯換算)的測定，係使用東曹(股)公司製HLC8220系統依照以下條件進行。In the present invention, the weight average molecular weight (in terms of polystyrene) of GPC was measured using the HLC 8220 system manufactured by Tosoh Corporation under the following conditions.
分離管柱：使用4根東曹(股)製TSKgelGMHHR -N。管柱溫度：40℃。移動層：和光純藥工業(股)製四氫呋喃。流速：1.0ml/分。試料濃度：1.0重量%。試料注入量：100微升。檢測器：差示折射計。Separation column: TSKgelGMH HR- N made of 4 Tosoh (stock) was used. Column temperature: 40 ° C. Moving layer: Heguang Pure Chemical Industry Co., Ltd. produces tetrahydrofuran. Flow rate: 1.0 ml/min. Sample concentration: 1.0% by weight. Sample injection amount: 100 μl. Detector: Differential refractometer.
預聚物(A)的NCO當量(β)之測定係依照JISK7301，將試料溶解於乾燥甲苯，添加過剩的二-n-丁基胺溶液使反應，以鹽酸標準溶液逆滴定残存的二-n-丁基胺而求得。The NCO equivalent (β) of the prepolymer (A) is determined according to JIS K7301, the sample is dissolved in dry toluene, the excess di-n-butylamine solution is added to react, and the residual di-n is counter-titrated with a hydrochloric acid standard solution. - butylamine is obtained.
預聚物(A)的黏度之測定係使用BM型黏度計(東京計器製)，在80℃使用樣品量200ml、2號或3號轉子來測定。The viscosity of the prepolymer (A) was measured using a BM-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 80 ° C using a sample of 200 ml, No. 2 or No. 3 rotor.
將含有預聚物(A)之主劑與異氰酸酯基反應性化合物(B)分別調整為內溫80℃與50℃，接著，混合主劑與硬化劑將成為胺基甲酸酯樹脂組成物的時點T0 當作基點，測定前述胺基甲酸酯樹脂組成物的黏度到達50000mPa‧s為止的時間T1 (單位；秒)，當作胺基甲酸酯樹脂組成物之反應性的測定結果。The main component containing the prepolymer (A) and the isocyanate-reactive compound (B) are respectively adjusted to an internal temperature of 80 ° C and 50 ° C, and then, the mixed main agent and the hardener are converted into a urethane resin composition. The time point T 0 was used as a base point, and the time T 1 (unit: second) until the viscosity of the urethane resin composition reached 50,000 mPa·s was measured, and the measurement result of the reactivity of the urethane resin composition was measured. .
然後，胺基甲酸酯樹脂組成物的黏度之測定係使用BM型黏度計(東京計器製)，在23℃之氛圍氣下以樣品量200ml、4號轉子每10秒加以測定。Then, the viscosity of the urethane resin composition was measured using a BM-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at a sample volume of 200 ml and an No. 4 rotor every 10 seconds under an atmosphere of 23 °C.
將前述預聚物(A)與含有水(C)及觸媒(D)之異氰酸酯基反應性化合物(B)分別置入二液混合澆鑄機的各自槽內，將預聚物(A)加溫至50~80℃，將反應性化合物(B)加溫至40~110℃，分別以二液混合澆鑄機進行混合。The prepolymer (A) and the isocyanate-reactive compound (B) containing water (C) and catalyst (D) are separately placed in respective tanks of a two-liquid mixing casting machine, and the prepolymer (A) is added. The temperature was 50 to 80 ° C, and the reactive compound (B) was heated to 40 to 110 ° C, and mixed by a two-liquid mixing casting machine.
將前述發泡反應液注入預先加溫至50~120℃之鑄模內。以注入於鑄模內之狀態，將發泡反應液加熱保持於適合的溫度範圍(例如，50~120℃之範圍)，使發泡、硬化，較佳為在50~120℃之模具內放置30分鐘~2小時後，將該成形品取出，以較佳為100~120℃、8~17小時的條件進行後硬化，作為成形品。The foaming reaction liquid is poured into a mold which is previously heated to 50 to 120 °C. The foaming reaction liquid is heated and maintained in a suitable temperature range (for example, in the range of 50 to 120 ° C) in a state of being injected into the mold to be foamed and hardened, preferably placed in a mold of 50 to 120 ° C. After the minute to 2 hours, the molded article is taken out, and post-hardened is preferably carried out at 100 to 120 ° C for 8 to 17 hours to obtain a molded article.
將前述成形品切片為適合的厚度之片狀。切片後之片厚只要依照硏磨目的加以設定即可，無特別限制，例如較佳為0.6~2.0mm之範圍。The molded article is sliced into a sheet having a suitable thickness. The sheet thickness after slicing is not particularly limited as long as it is set in accordance with the purpose of honing, and is preferably in the range of, for example, 0.6 to 2.0 mm.
將前述預聚物(A)與含有水(C)及觸媒(D)之反應性化合物(B)分別置入二液混合澆鑄機的各自槽內，將預聚物(A)加溫至50~80℃，將反應性化合物(B)加溫至40~110℃，分別以二液混合澆鑄機進行混合，在室溫下，注入上方開放的鑄模，使發泡。目視觀察，依照發泡狀態，將沒發生裂紋、發泡下方的膨脹者判定為成形性「良好」。The prepolymer (A) and the reactive compound (B) containing water (C) and catalyst (D) are separately placed in respective tanks of a two-liquid mixing casting machine, and the prepolymer (A) is heated to The reactive compound (B) was heated to 40 to 110 ° C at 50 to 80 ° C, and mixed by a two-liquid mixing casting machine, and injected into the upper open mold at room temperature to foam. It was visually observed that, in the foaming state, the crack was not generated, and the expander under the foaming was judged to be "good" in formability.
使用前述硏磨墊用2液型胺基甲酸酯樹脂組成物，以相同的樹脂組成物製作3個硏磨墊，各自浸漬於內溫設定為40℃、60℃、80℃之恆溫水槽中，測定2小時浸漬後硬度的經時變化。由硬度之經時變化，以下式算出硬度保持率，將硬度保持率70%以上的硏磨墊判定為耐久性(耐熱水性)良好，小於70%者判定為「不良」。Using the two-component urethane resin composition for the honing pad, three honing pads were prepared from the same resin composition, and each was immersed in a constant temperature water bath having an internal temperature of 40 ° C, 60 ° C, and 80 ° C. The change in hardness of the hardness after immersion for 2 hours was measured. The hardness retention ratio was calculated from the following formula, and the honing mat having a hardness retention ratio of 70% or more was judged to be excellent in durability (hot water resistance), and it was judged as "poor" when it was less than 70%.
硬度保持率(%)=2小時浸漬後之硬度/浸漬前之硬度×100Hardness retention rate (%) = 2 hours hardness after immersion / hardness before immersion × 100
依照JISK7312-1996(Taber磨耗試験)，評價耐摩耗性。耐摩耗性之評價基準係將摩耗減量200mg以下的硏磨墊判定為耐摩耗性良好。The abrasion resistance was evaluated in accordance with JIS K7312-1996 (Taber abrasion test). The evaluation criteria for the abrasion resistance were that the honing pad having a friction loss of 200 mg or less was judged to have good abrasion resistance.
依照JIS K 7312-1996(硬度試験)，進行彈簧硬度試験，以鑄模A進行評價。硬度之評價基準為硬度85(JIS A)以上的情形判定為「良好」、硬度85(JIS A)以下的情形判定為「不良」。According to JIS K 7312-1996 (hardness test), the spring hardness test was performed, and the mold A was evaluated. When the hardness is 8 (JIS A) or more, the hardness is determined to be "good", and the hardness is less than or equal to 85 (JIS A).
在具備氮導入管、冷卻用冷凝器、溫度計、攪拌機的1公升四口圓底燒瓶中，裝入作為聚異氰酸酯之聯甲苯胺二異氰酸酯(TODI)(a1)(日本曹達股份有限公司製)1068份，開始攪拌。接著，將1000份作為高分子量二醇(a21)之PTMG-1000(商品名，三菱化學股份有限公司製，聚伸丁二醇，Mn=1000)分次添加混合，在氮氣流下70℃進行2小時反應，然後將93份作為低分子量二醇(a22)之二乙二醇(DEG，三菱化學股份有限公司製，分子量106)分次添加混合，在氮氣流下70℃進行5小時反應，合成主劑之異氰酸酯基末端胺基甲酸酯預聚物(A-1)。Into a 1 liter four-neck round bottom flask equipped with a nitrogen inlet tube, a cooling condenser, a thermometer, and a stirrer, toluidine diisocyanate (TO1) (a1) (manufactured by Nippon Soda Co., Ltd.) 1068 as a polyisocyanate was charged. Serve, start stirring. Next, 1000 parts of PTMG-1000 (trade name, manufactured by Mitsubishi Chemical Corporation, polybutanediol, Mn = 1000) as a high molecular weight diol (a21) was added and mixed in portions, and the mixture was carried out at 70 ° C under a nitrogen stream. After an hour of reaction, 93 parts of diethylene glycol (DEG, manufactured by Mitsubishi Chemical Corporation, molecular weight 106) as a low molecular weight diol (a22) was added and mixed in portions, and the reaction was carried out at 70 ° C for 5 hours under a nitrogen stream to synthesize the main product. Isocyanate-terminated urethane prepolymer (A-1).
前述預聚物(A-1)在合成時之NCO/OH莫耳比(α)為2.15，前述預聚物(A-1)之NCO當量(β)為500，前述(α)與(β)的積(α×β)為1075。The NCO/OH molar ratio (α) of the prepolymer (A-1) at the time of synthesis is 2.15, and the NCO equivalent (β) of the prepolymer (A-1) is 500, and the aforementioned (α) and (β) The product (α × β) is 1075.
接著，在100份作為具有異氰酸酯基反應性化合物(B)之Pandex E-50中，調配0.6份作為發泡劑之離子交換水(C)、0.5份作為觸媒(D)之TOYOCAT-ET、及0.9份作為整泡劑之Toray Silicone SH-193，充分地攪拌混合，得到硬化劑之聚胺組成物(X-1)。Next, in 100 parts of Pandex E-50 having the isocyanate-reactive compound (B), 0.6 part of ion-exchanged water (C) as a foaming agent, 0.5 part of TOYOCAT-ET as a catalyst (D), And 0.9 parts of Toray Silicone SH-193 as a foam stabilizer, and thoroughly stirred and mixed to obtain a polyamine composition (X-1) of a hardener.
在容器中以預聚物(A-1)/聚胺組成物(X-1)=100/27重量比，將主劑之預聚物(A-1)與硬化劑之聚胺組成物(X-1)攪拌混合，將約350g注入預熱至50℃之模具(130mm×130mm×35mm)，立刻做成模具的蓋後，在50℃放置1小時，之後取出發泡成形品，將該發泡成形品在110℃進行16小時之後硬化，得到成形品。In the container, the prepolymer (A-1) / polyamine composition (X-1) = 100 / 27 by weight, the prepolymer (A-1) of the main agent and the polyamine composition of the hardener ( X-1) stirring and mixing, about 350 g of a mold (130 mm × 130 mm × 35 mm) preheated to 50 ° C, immediately after making a lid of the mold, and then standing at 50 ° C for 1 hour, and then taking out the foamed molded article, The foamed molded article was cured at 110 ° C for 16 hours to obtain a molded article.
將前述成形品以切片機切出約2mm厚，得到密度分布均勻之片狀聚胺基甲酸酯硏磨墊(P-1)。將該聚胺基甲酸酯硏磨墊(P-1)之物性(成形性、耐摩耗性、耐久性等)示於表1。The molded article was cut into a thickness of about 2 mm by a microtome to obtain a sheet-like polyurethane lining pad (P-1) having a uniform density distribution. The physical properties (formability, abrasion resistance, durability, and the like) of the polyurethane lining pad (P-1) are shown in Table 1.
在具備氮導入管、冷卻用冷凝器、溫度計、攪拌機的1公升四口圓底燒瓶裝入TODI(a1)(日本曹達股份有限公司製)968份，開始攪拌。接著，將1000份作為高分子量二醇(a21)之PTMG-1000分次添加混合，在氮氣流下70℃進行2小時反應，然後將67份作為低分子量二醇(a22)之DEG(三菱化學股份有限公司製)分次添加混合，在氮氣流下70℃進行5小時反應，合成主劑之預聚物(A-2)。A 1 liter four-neck round bottom flask equipped with a nitrogen inlet tube, a cooling condenser, a thermometer, and a stirrer was charged with 968 parts of TODI (a1) (manufactured by Nippon Soda Co., Ltd.), and stirring was started. Next, 1000 parts of PTMG-1000 as a high molecular weight diol (a21) was added and mixed in portions, and the reaction was carried out at 70 ° C for 2 hours under a nitrogen stream, and then 67 parts of DEG as a low molecular weight diol (a22) (Mitsubishi Chemical Co., Ltd.) The product was added in portions, and reacted at 70 ° C for 5 hours under a nitrogen stream to synthesize a prepolymer (A-2) of the main component.
前述預聚物(A-2)在合成時之NCO/OH莫耳比(α)為2.25，前述預聚物(A-2)之NCO當量(β)為500，前述(α)與(β)的積(α×β)為1111。The NCO/OH molar ratio (α) of the prepolymer (A-2) at the time of synthesis is 2.25, and the NCO equivalent (β) of the prepolymer (A-2) is 500, and the aforementioned (α) and (β) The product (α × β) is 1111.
接著，在100份作為反應性化合物(B)之Pandex E-50中調配0.6份作為發泡劑之離子交換水(C)、0.5份作為觸媒(D)之TOYOCAT-ET、及0.9份作為整泡劑之Toray Silicone SH-193，充分地攪拌混合，得到硬化劑之聚胺組成物(X-1)。Next, 0.6 parts of ion-exchanged water (C) as a foaming agent, 0.5 part of TOYOCAT-ET as a catalyst (D), and 0.9 parts were blended in 100 parts of Pandex E-50 as a reactive compound (B). Toray Silicone SH-193, a foam stabilizer, was thoroughly stirred and mixed to obtain a polyamine composition (X-1) of a hardener.
在容器中以預聚物(A-2)/聚胺組成物(X-1)=100/27重量比，攪拌混合主劑之預聚物(A-2)與硬化劑之聚胺組成物(X-1)，將約350g注入預熱至50℃之模具(130mm×130mm×35mm)，立刻做成模具的蓋後，在50℃放置1小時，之後取出發泡成形品，將該發泡成形品在110℃進行16小時之後硬化，得到成形品。Mixing the prepolymer (A-2) of the main component with the polyamine composition of the hardener in a weight ratio of the prepolymer (A-2) / polyamine composition (X-1) = 100 / 27 in a container (X-1), about 350 g of a mold (130 mm × 130 mm × 35 mm) preheated to 50 ° C was injected into the mold, and immediately placed at 50 ° C for 1 hour, and then the foamed molded article was taken out. The foam molded article was cured at 110 ° C for 16 hours to obtain a molded article.
將前述成形品以切片機切出約2mm厚，得到密度分布均勻之片狀聚胺基甲酸酯硏磨墊(P-2)。將該聚胺基甲酸酯硏磨墊(P-2)之物性(成形性、耐摩耗性、耐久性等)示於表1。The molded article was cut into a thickness of about 2 mm by a microtome to obtain a sheet-like polyurethane lining pad (P-2) having a uniform density distribution. The physical properties (formability, abrasion resistance, durability, and the like) of the polyurethane lining pad (P-2) are shown in Table 1.
在具備氮導入管、冷卻用冷凝器、溫度計、攪拌機的1公升四口圓底燒瓶裝入TODI(a1)(日本曹達股份有限公司製)904份，開始攪拌。接著，將1000份作為高分子量二醇(a21)之PTMG-1000分次添加混合，在氮氣流下70℃進行2小時反應，然後將67份作為低分子量二醇(a22)之DEG(三菱化學股份有限公司製)分次添加混合，在氮氣流下70℃進行5小時反應，合成主劑之預聚物(A-3)。In a 1 liter four-necked round bottom flask equipped with a nitrogen inlet tube, a cooling condenser, a thermometer, and a stirrer, 904 parts of TODI (a1) (manufactured by Nippon Soda Co., Ltd.) was placed, and stirring was started. Next, 1000 parts of PTMG-1000 as a high molecular weight diol (a21) was added and mixed in portions, and the reaction was carried out at 70 ° C for 2 hours under a nitrogen stream, and then 67 parts of DEG as a low molecular weight diol (a22) (Mitsubishi Chemical Co., Ltd.) The product was added in portions, and the reaction was carried out for 5 hours at 70 ° C under a nitrogen stream to synthesize a prepolymer (A-3) of the main component.
前述預聚物(A-3)在合成時之NCO/OH莫耳比(α)為2.10，前述預聚物(A-3)之NCO當量(β)為550，前述(α)與(β)的積(α×β)為1220。The NCO/OH molar ratio (α) of the prepolymer (A-3) at the time of synthesis is 2.10, and the NCO equivalent (β) of the prepolymer (A-3) is 550, and the aforementioned (α) and (β) The product (α × β) is 1220.
接著，在100份作為反應性化合物(B)之Pandex E-50中調配0.6份作為發泡劑之離子交換水(C)、0.5份作為觸媒(D)之TOYOCAT-ET、及0.9份作為整泡劑之Toray Silicone SH-193，充分地攪拌混合，得到硬化劑之聚胺組成物(X-1)。Next, 0.6 parts of ion-exchanged water (C) as a foaming agent, 0.5 part of TOYOCAT-ET as a catalyst (D), and 0.9 parts were blended in 100 parts of Pandex E-50 as a reactive compound (B). Toray Silicone SH-193, a foam stabilizer, was thoroughly stirred and mixed to obtain a polyamine composition (X-1) of a hardener.
在容器中以預聚物(A-3)/聚胺組成物(X-1)=100/25重量比，攪拌混合主劑之預聚物(A-3)與硬化劑之聚胺組成物(X-1)，將約350g注入預熱至50℃之模具(130mm×130mm×35mm)，立刻做成模具的蓋後，在50℃放置1小時，之後取出發泡成形品，將該發泡成形品在110℃進行16小時之後硬化，得到成形品。Mixing the prepolymer (A-3) of the main component with the polyamine composition of the hardener in a weight ratio of the prepolymer (A-3) / polyamine composition (X-1) = 100 / 25 in a container (X-1), about 350 g of a mold (130 mm × 130 mm × 35 mm) preheated to 50 ° C was injected into the mold, and immediately placed at 50 ° C for 1 hour, and then the foamed molded article was taken out. The foam molded article was cured at 110 ° C for 16 hours to obtain a molded article.
將前述成形品以切片機切出約2mm厚，得到密度分布均勻之片狀聚胺基甲酸酯硏磨墊(P-3)。將該聚胺基甲酸酯硏磨墊(P-3)之物性(成形性、耐摩耗性、耐久性等)示於表1。The molded article was cut into a thickness of about 2 mm by a microtome to obtain a sheet-like polyurethane lining pad (P-3) having a uniform density distribution. The physical properties (formability, abrasion resistance, durability, and the like) of the polyurethane lining pad (P-3) are shown in Table 1.
在具備氮導入管、冷卻用冷凝器、溫度計、攪拌機的1公升四口圓底燒瓶裝入TODI(a1)(日本曹達股份有限公司製)759份，開始攪拌。接著，將1000份作為高分子量二醇(a21)之PTMG-1000分次添加混合，在氮氣流下70℃進行2小時反應，然後將26份作為低分子量二醇(a22)之DEG(三菱化學股份有限公司製)分次添加混合，在氮氣流下70℃進行5小時反應，合成主劑之預聚物(A-4)。In a 1 liter four-necked round bottom flask equipped with a nitrogen inlet tube, a cooling condenser, a thermometer, and a stirrer, 759 parts of TODI (a1) (manufactured by Nippon Soda Co., Ltd.) was placed, and stirring was started. Next, 1000 parts of PTMG-1000 as a high molecular weight diol (a21) was added and mixed in portions, and the reaction was carried out at 70 ° C for 2 hours under a nitrogen stream, and then 26 parts of DEG (Mitsubishi Chemical Co., Ltd.) as a low molecular weight diol (a22) was added. The product was added in portions, and the reaction was carried out for 5 hours at 70 ° C under a nitrogen stream to synthesize a prepolymer (A-4) of the main component.
前述預聚物(A-4)在合成時之NCO/OH莫耳比(α)為2.30，前述預聚物(A-4)之NCO當量(β)為550，前述(α)與(β)的積(α×β)為1265。The NCO/OH molar ratio (α) of the prepolymer (A-4) at the time of synthesis is 2.30, and the NCO equivalent (β) of the prepolymer (A-4) is 550, and the aforementioned (α) and (β) The product (α × β) is 1265.
接著，在100份作為反應性化合物(B)之Pandex E-50中調配0.6份作為發泡劑之離子交換水(C)、0.5份作為觸媒(D)之TOYOCAT-ET、及0.9份作為整泡劑之Toray Silicone SH-193，充分地攪拌混合，得到硬化劑之聚胺組成物(X-1)。Next, 0.6 parts of ion-exchanged water (C) as a foaming agent, 0.5 part of TOYOCAT-ET as a catalyst (D), and 0.9 parts were blended in 100 parts of Pandex E-50 as a reactive compound (B). Toray Silicone SH-193, a foam stabilizer, was thoroughly stirred and mixed to obtain a polyamine composition (X-1) of a hardener.
在容器中以預聚物(A-4)/聚胺組成物(X-1)=100/25重量比，攪拌混合主劑之預聚物(A-4)與硬化劑之聚胺組成物(X-1)，將約350g注入預熱至50℃之模具(130mm×130mm×35mm)，立刻做成模具的蓋後，在50℃放置1小時，之後取出發泡成形品，將該發泡成形品在110℃進行16小時之後硬化，得到成形品。Mixing the prepolymer (A-4) of the main component with the polyamine composition of the hardener in a prepolymer (A-4) / polyamine composition (X-1) = 100 / 25 by weight ratio in a container (X-1), about 350 g of a mold (130 mm × 130 mm × 35 mm) preheated to 50 ° C was injected into the mold, and immediately placed at 50 ° C for 1 hour, and then the foamed molded article was taken out. The foam molded article was cured at 110 ° C for 16 hours to obtain a molded article.
將前述成形品以切片機切出約2mm厚，得到密度分布均勻之片狀聚胺基甲酸酯硏磨墊(P-4)。將該聚胺基甲酸酯硏磨墊(P-4)之物性(成形性、耐摩耗性、耐久性等)示於表1。The molded article was cut into a thickness of about 2 mm by a microtome to obtain a sheet-like polyurethane lining pad (P-4) having a uniform density distribution. The physical properties (formability, abrasion resistance, durability, and the like) of the polyurethane lining pad (P-4) are shown in Table 1.
在具備氮導入管、冷卻用冷凝器、溫度計、攪拌機的1公升四口圓底燒瓶裝入TODI(a1)(日本曹達股份有限公司製)1127份，開始攪拌。接著，將1000份作為高分子量二醇(a21)之PTMG-1000分次添加混合，在氮氣流下70℃進行2小時反應，然後將91份作為低分子量二醇(a22)之DEG(三菱化學股份有限公司製)分次添加混合，在氮氣流下70℃進行5小時反應，合成主劑之預聚物(A-5)。In a 1 liter four-neck round bottom flask equipped with a nitrogen inlet tube, a cooling condenser, a thermometer, and a stirrer, 1127 parts of TODI (a1) (manufactured by Nippon Soda Co., Ltd.) was placed, and stirring was started. Next, 1000 parts of PTMG-1000 as a high molecular weight diol (a21) was added and mixed in portions, and the reaction was carried out at 70 ° C for 2 hours under a nitrogen stream, and then 91 parts of DEG (Mitsubishi Chemical Co., Ltd.) as a low molecular weight diol (a22) was added. The product was added in portions, and the reaction was carried out for 5 hours at 70 ° C under a nitrogen stream to synthesize a prepolymer (A-5) of the main component.
前述預聚物(A-5)在合成時之NCO/OH莫耳比(α)為2.30，前述預聚物(A-5)之NCO當量(β)為460，前述(α)與(β)的積(α×β)為1058。The NCO/OH molar ratio (α) of the prepolymer (A-5) at the time of synthesis is 2.30, and the NCO equivalent (β) of the prepolymer (A-5) is 460, and the aforementioned (α) and (β) The product (α × β) is 1058.
接著，在100份作為反應性化合物(B)之Pandex E-50中調配0.6份作為發泡劑之離子交換水(C)、0.5份作為觸媒(D)之TOYOCAT-ET、及0.9份作為整泡劑之Toray Silicone SH-193，充分地攪拌混合，得到硬化劑之聚胺組成物(X-1)。Next, 0.6 parts of ion-exchanged water (C) as a foaming agent, 0.5 part of TOYOCAT-ET as a catalyst (D), and 0.9 parts were blended in 100 parts of Pandex E-50 as a reactive compound (B). Toray Silicone SH-193, a foam stabilizer, was thoroughly stirred and mixed to obtain a polyamine composition (X-1) of a hardener.
在容器中以預聚物(A-5)/聚胺組成物(X-1)=100/30重量比，攪拌混合主劑之預聚物(A-5)與硬化劑之聚胺組成物(X-1)，將約350g注入預熱至50℃之模具(130mm×130mm×35mm)，立刻做成模具的蓋後，在50℃放置1小時，之後取出發泡成形品，將該發泡成形品在110℃進行16小時之後硬化，得到成形品。Mixing the prepolymer (A-5) of the main component with the polyamine composition of the hardener in a weight ratio of the prepolymer (A-5) / polyamine composition (X-1) = 100 / 30 in a container (X-1), about 350 g of a mold (130 mm × 130 mm × 35 mm) preheated to 50 ° C was injected into the mold, and immediately placed at 50 ° C for 1 hour, and then the foamed molded article was taken out. The foam molded article was cured at 110 ° C for 16 hours to obtain a molded article.
將前述成形品以切片機切出約2mm厚，得到密度分布均勻之片狀聚胺基甲酸酯硏磨墊(P-5)。將該聚胺基甲酸酯硏磨墊(P-5)之物性(成形性、耐摩耗性、耐久性等)示於表1。The molded article was cut into a thickness of about 2 mm by a microtome to obtain a sheet-like polyurethane lining pad (P-5) having a uniform density distribution. The physical properties (formability, abrasion resistance, durability, and the like) of the polyurethane lining pad (P-5) are shown in Table 1.
在具備氮導入管、冷卻用冷凝器、溫度計、攪拌機的1公升四口圓底燒瓶裝入作為聚異氰酸酯之聯甲苯胺二異氰酸酯(TODI)(a1)(日本曹達股份有限公司製)913份，開始攪拌。接著，將1000份作為二醇之PTMG-650(商品名，三菱化學股份有限公司製，聚伸丁二醇，Mn=650)分次添加混合，在氮氣流下70℃進行5小時反應，合成主劑之異氰酸酯基末端胺基甲酸酯預聚物(A-6)。913 parts of toluidine diisocyanate (TO1) (a1) (manufactured by Nippon Soda Co., Ltd.) as a polyisocyanate was placed in a 1 liter four-neck round bottom flask equipped with a nitrogen inlet tube, a cooling condenser, a thermometer, and a stirrer. Start stirring. Next, 1000 parts of PTMG-650 (trade name, manufactured by Mitsubishi Chemical Corporation, polybutanediol, Mn = 650) as a diol was added and mixed in portions, and the reaction was carried out at 70 ° C for 5 hours under a nitrogen stream to synthesize the main product. Isocyanate-terminated urethane prepolymer (A-6).
前述預聚物(A-6)在合成時之NCO/OH莫耳比(α)為2.25，前述預聚物(A-6)之NCO當量(β)為500，前述(α)與(β)的積(α×β)為1125。The NCO/OH molar ratio (α) of the prepolymer (A-6) at the time of synthesis is 2.25, and the NCO equivalent (β) of the prepolymer (A-6) is 500, and the aforementioned (α) and (β) The product (α × β) is 1125.
接著，在100份作為具有異氰酸酯基反應性化合物(B)之Pandex E-50中，調配0.6份作為發泡劑之離子交換水(C)、0.5份作為觸媒(D)之TOYOCAT-ET、及0.9份作為整泡劑之Toray Silicone SH-193，充分地攪拌混合，得到硬化劑之聚胺組成物(X-1)。Next, in 100 parts of Pandex E-50 having the isocyanate-reactive compound (B), 0.6 part of ion-exchanged water (C) as a foaming agent, 0.5 part of TOYOCAT-ET as a catalyst (D), And 0.9 parts of Toray Silicone SH-193 as a foam stabilizer, and thoroughly stirred and mixed to obtain a polyamine composition (X-1) of a hardener.
在容器中以預聚物(A-6)/聚胺組成物(X-1)=100/27重量比，攪拌混合主劑之預聚物(A-6)與硬化劑之聚胺組成物(X-1)，將約350g注入預熱至50℃之模具(130mm×130mm×35mm)，立刻做成模具的蓋後，在50℃放置1小時，之後取出發泡成形品，將該發泡成形品在110℃進行16小時之後硬化，得到成形品。Mixing the prepolymer (A-6) of the main component with the polyamine composition of the hardener in a weight ratio of the prepolymer (A-6) / polyamine composition (X-1) = 100 / 27 in a container (X-1), about 350 g of a mold (130 mm × 130 mm × 35 mm) preheated to 50 ° C was injected into the mold, and immediately placed at 50 ° C for 1 hour, and then the foamed molded article was taken out. The foam molded article was cured at 110 ° C for 16 hours to obtain a molded article.
將前述成形品以切片機切出約2mm厚，得到密度分布均勻之片狀聚胺基甲酸酯硏磨墊(P-6)。將該聚胺基甲酸酯硏磨墊(P-6)之物性(成形性、耐摩耗性、耐久性等)示於表1。The molded article was cut into a thickness of about 2 mm by a microtome to obtain a sheet-like polyurethane lining pad (P-6) having a uniform density distribution. The physical properties (formability, abrasion resistance, durability, and the like) of the polyurethane lining pad (P-6) are shown in Table 1.
在具備氮導入管、冷卻用冷凝器、溫度計、攪拌機的1公升四口圓底燒瓶裝入作為聚異氰酸酯之Cosmonate T-80(商品名，三井化學聚胺基甲酸酯股份有限公司製，甲苯二異氰酸酯(TDI)之2,4-異構物與2,6-異構物的80:20之混合物)1117份，開始攪拌。接著，將1000份作為高分子量二醇(a21)之PTMG-1000(商品名，三菱化學股份有限公司製，聚伸丁二醇，Mn=1000)分次添加混合，在氮氣流下70℃進行2小時反應，然後將268份作為低分子量二醇(a22)之二乙二醇(DEG，三菱化學股份有限公司製，分子量106)分次添加混合，在氮氣流下70℃進行5小時反應，合成主劑之異氰酸酯基末端胺基甲酸酯預聚物(A-7)。Cosmonate T-80 (trade name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., toluene) was placed in a 1 liter four-neck round bottom flask equipped with a nitrogen inlet tube, a cooling condenser, a thermometer, and a stirrer. A mixture of 1,117 parts of a 2,4-isomer of diisocyanate (TDI) and a 2:6-isomer of 80:20 was started to stir. Next, 1000 parts of PTMG-1000 (trade name, manufactured by Mitsubishi Chemical Corporation, polybutanediol, Mn = 1000) as a high molecular weight diol (a21) was added and mixed in portions, and the mixture was carried out at 70 ° C under a nitrogen stream. After reacting for an hour, 268 parts of diethylene glycol (DEG, manufactured by Mitsubishi Chemical Corporation, molecular weight 106) as a low molecular weight diol (a22) was added and mixed in portions, and the reaction was carried out at 70 ° C for 5 hours under a nitrogen stream to synthesize the main product. Isocyanate-terminated urethane prepolymer (A-7).
前述預聚物(A-7)在合成時之NCO/OH莫耳比(α)為1.85，前述預聚物(A-7)之NCO當量(β)為400，前述(α)與(β)的積(α×β)為740。The NCO/OH molar ratio (α) of the prepolymer (A-7) at the time of synthesis is 1.85, and the NCO equivalent (β) of the prepolymer (A-7) is 400, and the aforementioned (α) and (β) The product (α × β) is 740.
接著，在100份作為具有異氰酸酯基反應性化合物(B)之Pandex E-50中調配0.5份作為發泡劑之離子交換水(C)、0.3份作為觸媒(D)之TOYOCAT-ET、及0.9份作為整泡劑之Toray Silicone SH-193，充分地攪拌混合，得到硬化劑之聚胺組成物(X-2)。Next, in 100 parts of Pandex E-50 having an isocyanate-reactive compound (B), 0.5 part of ion-exchanged water (C) as a foaming agent, 0.3 part of TOYOCAT-ET as a catalyst (D), and 0.9 parts of Toray Silicone SH-193 as a foam stabilizer was sufficiently stirred and mixed to obtain a polyamine composition (X-2) of a hardener.
在容器中以預聚物(A-7)/聚胺組成物(X-2)=100/30重量比，攪拌混合主劑之預聚物(A-7)與硬化劑之聚胺組成物(X-2)，將約350g注入預熱至50℃之模具(130mm×130mm×35mm)，立刻做成模具的蓋後，在50℃放置1小時，之後取出發泡成形品，將該發泡成形品在110℃進行16小時之後硬化，得到成形品。The polyamine composition of the prepolymer (A-7) and the hardener mixed with the prepolymer (A-7)/polyamine composition (X-2) = 100/30 by weight in a container (X-2), about 350 g of a mold (130 mm × 130 mm × 35 mm) preheated to 50 ° C was injected into the mold, and immediately placed at 50 ° C for 1 hour, and then the foamed molded article was taken out. The foam molded article was cured at 110 ° C for 16 hours to obtain a molded article.
將前述成形品以切片機切出約2mm厚，得到片狀之聚胺基甲酸酯硏磨墊(P-7)。將該聚胺基甲酸酯硏磨墊(P-7)之物性(成形性、耐摩耗性、耐久性等)示於表2。由其結果得知耐久性(耐熱水性)為不佳。The molded article was cut into a thickness of about 2 mm by a microtome to obtain a sheet-shaped polyurethane lining pad (P-7). The physical properties (formability, abrasion resistance, durability, and the like) of the polyurethane lining pad (P-7) are shown in Table 2. From the results, it was found that durability (hot water resistance) was poor.
在具備氮導入管、冷卻用冷凝器、溫度計、攪拌機的1公升四口圓底燒瓶裝入TODI(a1)(日本曹達股份有限公司製)904份，開始攪拌。接著，將1000份作為高分子量二醇(a21)之PTMG-1000(商品名，三菱化學股份有限公司製，聚伸丁二醇，Mn=1000)分次添加混合，在氮氣流下70℃進行2小時反應，然後將67份作為低分子量二醇(a22)之二乙二醇(DEG，三菱化學股份有限公司製，分子量106)分次添加混合，在氮氣流下70℃進行5小時反應，合成主劑之預聚物(A-8)。In a 1 liter four-necked round bottom flask equipped with a nitrogen inlet tube, a cooling condenser, a thermometer, and a stirrer, 904 parts of TODI (a1) (manufactured by Nippon Soda Co., Ltd.) was placed, and stirring was started. Next, 1000 parts of PTMG-1000 (trade name, manufactured by Mitsubishi Chemical Corporation, polybutanediol, Mn = 1000) as a high molecular weight diol (a21) was added and mixed in portions, and the mixture was carried out at 70 ° C under a nitrogen stream. After reacting for an hour, 67 parts of diethylene glycol (DEG, manufactured by Mitsubishi Chemical Corporation, molecular weight 106) as a low molecular weight diol (a22) was added and mixed in portions, and the reaction was carried out at 70 ° C for 5 hours under a nitrogen stream to synthesize the main product. Prepolymer (A-8).
前述預聚物(A-8)在合成時之NCO/OH莫耳比(α)為2.10，前述預聚物(A-8)之NCO當量(β)為500，前述(α)與(β)的積(α×β)為1050。The NCO/OH molar ratio (α) of the prepolymer (A-8) at the time of synthesis is 2.10, and the NCO equivalent (β) of the prepolymer (A-8) is 500, and the aforementioned (α) and (β) The product (α × β) is 1050.
預聚物(A-8)係在合成時發生凝膠化，無法得到良好的性能。結果示於表2。The prepolymer (A-8) gelled during the synthesis, and good performance could not be obtained. The results are shown in Table 2.
在具備氮導入管、冷卻用冷凝器、溫度計、攪拌機的1公升四口圓底燒瓶裝入TODI(a1)(日本曹達股份有限公司製)806份，開始攪拌。接著，將1000份作為高分子量二醇(a21)之PTMG-1000分次添加混合，在氮氣流下70℃進行2小時反應，然後將23份作為低分子量二醇(a22)之DEG(三菱化學股份有限公司製)分次添加混合，在氮氣流下70℃進行5小時反應，合成主劑之預聚物(A-9)。In a 1 liter four-necked round bottom flask equipped with a nitrogen inlet tube, a cooling condenser, a thermometer, and a stirrer, 806 parts of TODI (a1) (manufactured by Nippon Soda Co., Ltd.) was placed, and stirring was started. Next, 1000 parts of PTMG-1000 as a high molecular weight diol (a21) was added and mixed in portions, and the reaction was carried out at 70 ° C for 2 hours under a nitrogen stream, and then 23 parts of DEG as a low molecular weight diol (a22) (Mitsubishi Chemical Co., Ltd.) The product was added in portions, and reacted at 70 ° C for 5 hours under a nitrogen stream to synthesize a prepolymer (A-9) of the main component.
前述預聚物(A-9)在合成時之NCO/OH莫耳比(α)為2.50，前述預聚物(A-9)之NCO當量(β)為500，前述(α)與(β)的積(α×β)為1250。The NCO/OH molar ratio (α) of the prepolymer (A-9) at the time of synthesis is 2.50, and the NCO equivalent (β) of the prepolymer (A-9) is 500, and the aforementioned (α) and (β) The product (α × β) is 1250.
接著，在100份作為反應性化合物(B)之Pandex E-50中調配0.6份作為發泡劑之離子交換水(C)、0.5份作為觸媒(D)之TOYOCAT-ET、及0.9份作為整泡劑之Toray Silicone SH-193，充分地攪拌混合，得到硬化劑之聚胺組成物(X-1)。Next, 0.6 parts of ion-exchanged water (C) as a foaming agent, 0.5 part of TOYOCAT-ET as a catalyst (D), and 0.9 parts were blended in 100 parts of Pandex E-50 as a reactive compound (B). Toray Silicone SH-193, a foam stabilizer, was thoroughly stirred and mixed to obtain a polyamine composition (X-1) of a hardener.
在容器中以預聚物(A-9)/聚胺組成物(X-1)=100/27重量比，攪拌混合主劑之預聚物(A-9)與硬化劑之聚胺組成物(X-1)將約350g注入預熱至50℃之模具(130mm×130mm×35mm)，立刻做成模具的蓋後，在50℃放置1小時，之後取出發泡成形品，將該發泡成形品在110℃進行16小時之後硬化，得到成形品。The polyamine composition of the prepolymer (A-9) and the hardener mixed with the prepolymer (A-9)/polyamine composition (X-1) = 100/27 by weight in a container (X-1) About 350 g of a mold (130 mm × 130 mm × 35 mm) preheated to 50 ° C was poured into a mold, and immediately placed at 50 ° C for 1 hour, and then the foamed molded article was taken out, and the foam was foamed. The molded article was cured at 110 ° C for 16 hours to obtain a molded article.
所得成形品發生裂紋與發泡下方的膨脹，無法得到良好的片狀聚胺基甲酸酯硏磨墊(P-9)。結果示於表2。The obtained molded product was cracked and expanded under foaming, and a favorable sheet-like polyurethane lining pad (P-9) could not be obtained. The results are shown in Table 2.
在具備氮導入管、冷卻用冷凝器、溫度計、攪拌機的1公升四口圓底燒瓶裝入TODI(a1)(日本曹達股份有限公司製)1176份，開始攪拌。接著，將1000份作為高分子量二醇(a21)之PTMG-1000分次添加混合，在氮氣流下70℃進行2小時反應，然後將143份作為低分子量二醇(a22)之DEG(三菱化學股份有限公司製)分次添加混合，在氮氣流下70℃進行5小時反應，合成主劑之預聚物(A-10)。A 1 liter four-neck round bottom flask equipped with a nitrogen inlet tube, a cooling condenser, a thermometer, and a stirrer was charged with 1176 parts of TODI (a1) (manufactured by Nippon Soda Co., Ltd.), and stirring was started. Next, 1000 parts of PTMG-1000 as a high molecular weight diol (a21) was added and mixed in portions, and the reaction was carried out at 70 ° C for 2 hours under a nitrogen stream, and then 143 parts of DEG (Mitsubishi Chemical Co., Ltd.) as a low molecular weight diol (a22) was used. The product was added in portions, and reacted at 70 ° C for 5 hours under a nitrogen stream to synthesize a prepolymer (A-10) of the main component.
前述預聚物(A-10)在合成時之NCO/OH莫耳比(α)為2.00，前述預聚物(A-10)之NCO當量(β)為550，前述(α)與(β)的積(α×β)為1100。The NCO/OH molar ratio (α) of the prepolymer (A-10) at the time of synthesis is 2.00, and the NCO equivalent (β) of the prepolymer (A-10) is 550, and the aforementioned (α) and (β) The product (α × β) is 1100.
如表2所示，預聚物(A-10)係在合成時產生凝膠化，無法得到良好的性能。結果示於表2。As shown in Table 2, the prepolymer (A-10) was gelated at the time of synthesis, and good properties could not be obtained. The results are shown in Table 2.
在具備氮導入管、冷卻用冷凝器、溫度計、攪拌機的1公升四口圓底燒瓶裝入TODI(a1)(日本曹達股份有限公司製)719份，開始攪拌。接著，1000份作為二醇之PTMG-1000分次添加混合，在氮氣流下70℃進行5小時反應，合成主劑之預聚物(A-11)。In a 1 liter four-necked round bottom flask equipped with a nitrogen inlet tube, a cooling condenser, a thermometer, and a stirrer, 719 parts of TODI (a1) (manufactured by Nippon Soda Co., Ltd.) was placed, and stirring was started. Next, 1000 parts of PTMG-1000 as a diol was added and mixed in portions, and the reaction was carried out at 70 ° C for 5 hours under a nitrogen stream to synthesize a prepolymer (A-11) of a main component.
前述預聚物(A-11)在合成時之NCO/OH莫耳比(α)為2.72，前述預聚物(A-11)之NCO當量(β)為500，前述(α)與(β)的積(α×β)為1360。The NCO/OH molar ratio (α) of the prepolymer (A-11) at the time of synthesis is 2.72, and the NCO equivalent (β) of the prepolymer (A-11) is 500, and the aforementioned (α) and (β) The product (α × β) is 1360.
接著，在100份作為反應性化合物(B)之Pandex E-50中調配0.6份作為發泡劑之離子交換水(C)、0.5份作為觸媒(D)之TOYOCAT-ET、及0.9份作為整泡劑之Toray Silicone SH-193，充分地攪拌混合，得到硬化劑之聚胺組成物(X-1)。Next, 0.6 parts of ion-exchanged water (C) as a foaming agent, 0.5 part of TOYOCAT-ET as a catalyst (D), and 0.9 parts were blended in 100 parts of Pandex E-50 as a reactive compound (B). Toray Silicone SH-193, a foam stabilizer, was thoroughly stirred and mixed to obtain a polyamine composition (X-1) of a hardener.
在容器中以預聚物(A-11)/聚胺組成物(X-1)=100/27重量比，攪拌混合主劑之預聚物(A-11)與硬化劑之聚胺組成物(X-1)，將約350g注入預熱至50℃之模具(130mm×130mm×35mm)，立刻做成模具的蓋後，在50℃放置1小時，之後取出發泡成形品，將該發泡成形品在110℃進行16小時之後硬化，得到成形品。Mixing the prepolymer (A-11) of the main component with the polyamine composition of the hardener in a weight ratio of the prepolymer (A-11) / polyamine composition (X-1) = 100 / 27 in a container (X-1), about 350 g of a mold (130 mm × 130 mm × 35 mm) preheated to 50 ° C was injected into the mold, and immediately placed at 50 ° C for 1 hour, and then the foamed molded article was taken out. The foam molded article was cured at 110 ° C for 16 hours to obtain a molded article.
所得成形品發生裂紋與發泡下方的膨脹，無法得到良好的片狀聚胺基甲酸酯硏磨墊(P-11)。結果示於表2。The obtained molded article was cracked and expanded under foaming, and a favorable sheet-like polyurethane lining pad (P-11) could not be obtained. The results are shown in Table 2.
本發明之硏磨墊用2液型胺基甲酸酯樹脂組成物係作業時反應性的控制為容易且成形性優異，能夠形成均勻且微細形狀之發泡胞。In the two-liquid urethane resin composition system for the honing pad of the present invention, the control of the reactivity is easy and the moldability is excellent, and a foamed cell having a uniform and fine shape can be formed.
又，本發明之聚胺基甲酸酯硏磨墊在硏磨操作時因溫度上昇導致之硏磨墊硬度(彈性模數)改變為小，耐久性(耐熱水性等)、耐摩耗性、成形性(產率、成形不均等)優良，可用於例如，液晶顯示器(LCD)用玻璃基板、硬碟(HDD)用玻璃基板、記錄裝置用玻璃碟片、光學用透鏡、矽晶圓、半導體元件等之要求高度表面平坦性的玻璃材料之精密硏磨。Further, the polyurethane lining pad of the present invention has a small change in the hardness (elastic modulus) of the honing pad due to an increase in temperature during the honing operation, durability (heat-resistant water resistance, etc.), abrasion resistance, and formation. It is excellent in properties (yield, uneven molding, etc.) and can be used, for example, in a glass substrate for a liquid crystal display (LCD), a glass substrate for a hard disk (HDD), a glass disk for a recording device, an optical lens, a germanium wafer, and a semiconductor element. Such as the precision honing of glass materials requiring high surface flatness.
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