TW202104326A - Resin molded body - Google Patents

Resin molded body Download PDF

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TW202104326A
TW202104326A TW109113221A TW109113221A TW202104326A TW 202104326 A TW202104326 A TW 202104326A TW 109113221 A TW109113221 A TW 109113221A TW 109113221 A TW109113221 A TW 109113221A TW 202104326 A TW202104326 A TW 202104326A
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molded body
resin
mass
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樋口大地
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日商Ｄｉｃ股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N19/00—Investigating materials by mechanical methods
    • G01N19/02—Measuring coefficient of friction between materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N3/08—Investigating strength properties of solid materials by application of mechanical stress by applying steady tensile or compressive forces

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Automation & Control Theory (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Investigating Strength Of Materials By Application Of Mechanical Stress (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention addresses the problem of achieving both flexibility and scratch resistance. A resin molded body according to the present invention has a 100% modulus of 5 MPa or less, a hysteresis loss during 100% stretch recovery of 20% or less, and a dynamic friction force of 2 kN or less.

Description

樹脂成形體Resin molded body

本發明係關於一種樹脂成形體。The present invention relates to a resin molded body.

樹脂成形體係具有柔軟性、彈性等優異性質，而被使用在汽車零件、家電零件、包裝材料、皮革狀片、印刷輥等各種用途。The resin molding system has excellent properties such as flexibility and elasticity, and is used in various applications such as automobile parts, home appliance parts, packaging materials, leather-like sheets, and printing rollers.

作為這種胺基甲酸酯樹脂組成物，已有提案一種包含主劑與硬化劑的胺基甲酸酯樹脂組成物，其中該主劑係使不具有芳香環之多元醇、與具有芳香環之聚異氰酸酯反應而製造異氰酸酯基末端的胺基甲酸酯預聚物，並使該胺基甲酸酯預聚物與分支二醇反應而成(例如參照專利文獻1)。 [先前技術文獻] [專利文獻]As such a urethane resin composition, a urethane resin composition containing a main agent and a hardener has been proposed, wherein the main agent is a polyhydric alcohol without an aromatic ring and a polyol with an aromatic ring. The polyisocyanate is reacted to produce an isocyanate group-terminated urethane prepolymer, and the urethane prepolymer is reacted with a branched diol (for example, refer to Patent Document 1). [Prior Technical Literature] [Patent Literature]

專利文獻1　日本特開2018-150421號公報Patent Document 1 　 JP 2018-150421 A

[發明所欲解決之課題][The problem to be solved by the invention]

然而，在以往所知的樹脂成形體中，會有無法充分滿足兼具柔軟性、與耐擦傷性之情形。本發明係鑒於前述事情而完成者，以兼具柔軟性、與耐擦傷性為課題。 [用以解決課題之手段]However, in conventionally known resin moldings, there are cases where it is not possible to sufficiently satisfy both flexibility and scratch resistance. The present invention was completed in view of the foregoing matters, and has the subject of combining flexibility and scratch resistance. [Means to solve the problem]

以往，為了提升耐擦傷性，已有許多提高樹脂成形體的硬度之嘗試。然而，提高樹脂成形體的硬度之情形，在樹脂本身的硬度亦有上限，另一方面，一旦樹脂被破壞，則形狀不會回復，所以留下刮痕，結果有無法充分提升耐擦傷性之情形。本發明人等，以與這種以往嘗試提高樹脂硬度相反的構思，構想了一邊抑制樹脂成形體的硬度，並且提高變形回復率，進而提高樹脂成形體表面的平滑性。發現若如此進行，則由於抑制了硬度，而儘管會成為柔軟的樹脂，但提高了變形回復率，因而在樹脂表面不會留下刮痕，其結果可得到可兼具柔軟性與耐擦傷性之樹脂成形體，而完成本發明。In the past, in order to improve the scratch resistance, there have been many attempts to increase the hardness of the resin molded body. However, in the case of increasing the hardness of the resin molded body, the hardness of the resin itself also has an upper limit. On the other hand, once the resin is broken, the shape does not recover, so scratches are left. As a result, the scratch resistance cannot be sufficiently improved. situation. The inventors of the present invention, based on the concept contrary to this conventional attempt to increase the hardness of the resin, conceived that while suppressing the hardness of the resin molded body, increasing the deformation recovery rate, and further improving the smoothness of the surface of the resin molded body. It was found that if this is done, the hardness is suppressed, and although it becomes a soft resin, the deformation recovery rate is increased, so no scratches are left on the resin surface. As a result, it is possible to obtain a combination of flexibility and scratch resistance. The resin molded body, and completed the present invention.

亦即，本發明之樹脂成形體，係利用下述方法所測定之100%模數為5MPa以下，利用下述方法所測定之100%伸長回復時的磁滯損失為20%以下，且利用下述方法所測定之動摩擦力為2kN以下。That is, the resin molded body of the present invention has a 100% modulus measured by the following method is 5 MPa or less, and the hysteresis loss at 100% elongation recovery measured by the following method is 20% or less. The dynamic friction force measured by the above method is less than 2kN.

[100%模數之測定方法] 將成形為厚度30μm、寬5mm、長度50mm，且在溫度23℃的環境下，使用拉伸試驗機，以初期的卡盤間距離40mm、拉伸速度10mm/秒之條件進行伸長，並進行了100%伸長時的應力，設為100%模數。[Method of measuring 100% modulus] It was formed into a thickness of 30μm, a width of 5mm, and a length of 50mm, and in an environment with a temperature of 23°C, using a tensile testing machine, the initial distance between the chucks was 40mm and the tensile speed was 10mm/sec. The stress at 100% elongation is set to 100% modulus.

[100%伸長回復時的磁滯損失之測定方法] 成形為厚度30μm、寬5mm、長度50mm，且在溫度23℃的環境下，使用拉伸試驗機，以初期的卡盤間距離40mm、伸長速度10mm/秒之條件進行伸長，進行了100%伸長後，立即以卡盤間距離40mm、伸縮速度10mm/秒之條件使其伸縮。此時，將從所施加的負載與變形量之圖表的積分值，自試驗片在拉伸時被施予的熱量與在拉回時試驗片所放出的熱量之差所求出之熱量的損失比例，設為磁滯損失。[Measuring method of hysteresis loss at 100% elongation recovery] It was formed into a thickness of 30μm, a width of 5mm, and a length of 50mm, and under the environment of a temperature of 23℃, using a tensile testing machine, the initial distance between the chucks was 40mm and the elongation speed was 10mm/sec. After that, immediately expand and contract under the conditions of a distance between the chucks of 40 mm and an expansion speed of 10 mm/sec. At this time, from the integrated value of the graph of the applied load and the amount of deformation, the heat loss is calculated from the difference between the heat applied to the test piece when it is stretched and the heat released by the test piece when it is pulled back The ratio is set as the hysteresis loss.

[摩擦力之測定方法] 將成形為厚度30μm、寬5mm、長度50mm，且在溫度23℃的環境下，使負載為200gf，並使用直徑10mm的不鏽鋼製球壓頭，而以試驗速度120cm/分鐘之條件所測定之摩擦力，設為動摩擦力。 [發明的效果][Measurement method of friction force] It is formed into a thickness of 30μm, a width of 5mm, and a length of 50mm. The friction is measured under the conditions of a test speed of 120cm/min with a load of 200gf at a temperature of 23°C and a stainless steel ball indenter with a diameter of 10mm. Force, set as dynamic friction force. [Effects of the invention]

本發明之樹脂成形體可兼具柔軟性、與耐擦傷性。The resin molded body of the present invention can have both flexibility and scratch resistance.

[用以實施發明之態樣][Pattern for implementing the invention]

前述樹脂成形體，係利用下述方法所測定之100%模數為5MPa。前述100%模數，係較佳為4.5MPa以下，更佳為4.0MPa以下，進一步較佳為2.0MPa以上，例如為2.5MPa以上，較佳為3.0MPa以上。The aforementioned resin molded body has a 100% modulus of 5 MPa as measured by the following method. The aforementioned 100% modulus is preferably 4.5 MPa or less, more preferably 4.0 MPa or less, still more preferably 2.0 MPa or more, for example, 2.5 MPa or more, preferably 3.0 MPa or more.

[100%模數之測定方法] 將成形為厚度30μm、寬5mm、長度50mm，且在溫度23℃的環境下，使用拉伸試驗機，以初期的卡盤間距離40mm、拉伸速度10mm/秒之條件進行伸長，並進行了100%伸長時的應力，設為100%模數。[Method of measuring 100% modulus] It was formed into a thickness of 30μm, a width of 5mm, and a length of 50mm, and in an environment with a temperature of 23°C, using a tensile testing machine, the initial distance between the chucks was 40mm and the tensile speed was 10mm/sec. The stress at 100% elongation is set to 100% modulus.

前述樹脂成形體，係利用下述方法所測定之100%伸長回復時的磁滯損失為20%以下。前述磁滯損失，係較佳為10%以下，更佳為5%以下，進一步較佳為1%以下，且下限係較佳為0%，例如可容許為5%以上，進一步亦可容許為10%以上。The aforementioned resin molded body has a hysteresis loss at 100% elongation recovery measured by the following method of 20% or less. The aforementioned hysteresis loss is preferably 10% or less, more preferably 5% or less, still more preferably 1% or less, and the lower limit is preferably 0%, for example, allowable 5% or more, and further allowable More than 10%.

[100%伸長回復時的磁滯損失之測定方法] 成形為厚度30μm、寬5mm、長度50mm，且在溫度23℃的環境下，使用拉伸試驗機，以初期的卡盤間距離40mm、伸長速度10mm/秒之條件進行伸長，進行了100%伸長後，立即以卡盤間距離40mm、伸縮速度10mm/秒之條件使其伸縮。此時，將從所施加的負載與變形量之圖表的積分值，自試驗片在拉伸時被施予的熱量與在拉回時試驗片所放出的熱量之差所求出之熱量的損失比例，設為磁滯損失。[Measuring method of hysteresis loss at 100% elongation recovery] It was formed into a thickness of 30μm, a width of 5mm, and a length of 50mm, and under the environment of a temperature of 23℃, using a tensile testing machine, the initial distance between the chucks was 40mm and the elongation speed was 10mm/sec. After that, immediately expand and contract under the conditions of a distance between the chucks of 40 mm and an expansion speed of 10 mm/sec. At this time, from the integrated value of the graph of the applied load and the amount of deformation, the heat loss is calculated from the difference between the heat applied to the test piece when it is stretched and the heat released by the test piece when it is pulled back The ratio is set as the hysteresis loss.

前述樹脂成形體，係利用下述方法所測定之動摩擦力為2kN以下。前述動摩擦力，係較佳為1kN以下，更佳為0.5kN以下，進一步較佳為0.1kN以下，例如可容許為0.1kN以上，進一步亦可容許為0.5kN以上。The aforementioned resin molded body has a dynamic friction force of 2 kN or less measured by the following method. The aforementioned dynamic friction force is preferably 1 kN or less, more preferably 0.5 kN or less, still more preferably 0.1 kN or less, for example, allowable 0.1 kN or more, and further allowable 0.5 kN or more.

[摩擦力之測定方法] 將成形為厚度30μm、寬5mm、長度50mm，且在溫度23℃的環境下，使負載為200gf，並使用直徑10mm的不鏽鋼製球壓頭，而以試驗速度120cm/分鐘之條件所測定之摩擦力，設為動摩擦力。[Measurement method of friction force] It is formed into a thickness of 30μm, a width of 5mm, and a length of 50mm. The friction is measured under the conditions of a test speed of 120cm/min with a load of 200gf at a temperature of 23°C and a stainless steel ball indenter with a diameter of 10mm. Force, set as dynamic friction force.

前述樹脂成形體的厚度，係較佳為1μm以上，較佳為3μm以上，進一步較佳為5μm以上，且較佳為200μm以下，更佳為100μm以下，進一步較佳為50μm以下。The thickness of the aforementioned resin molded body is preferably 1 μm or more, more preferably 3 μm or more, more preferably 5 μm or more, and preferably 200 μm or less, more preferably 100 μm or less, and still more preferably 50 μm or less.

前述100%模數及前述磁滯損失，係可藉由調整例如在樹脂成形體所含之樹脂的分子鏈中具剛直性的部位與具柔軟性的部位之比例、或剛直性、柔軟性的程度、交聯度等而達成。例如，從降低前述100%模數之觀點來看，前述樹脂較佳為具有具柔軟性的部位(軟鏈段)，前述具柔軟性的部位具有玻璃轉移溫度之情形，該玻璃轉移溫度係例如為20℃以下，較佳為0℃以下、-5℃以下、-15℃以下、-25℃以下、-35℃以下。從降低前述磁滯損失之觀點來看，前述樹脂較佳為具有具剛直性的部位(硬鏈段)。前述具剛直性的部位(硬鏈段)為物理或化學上交聯軟鏈段的部位，而就物理交聯而言，可列舉利用可形成氫鍵之官能基(胺基甲酸酯鍵基、脲鍵基等)的交聯，而就化學交聯而言，可列舉利用交聯劑(多官能單體、硫化劑等)的交聯。化學交聯能夠可逆地形成，另一方面，物理交聯若變形量變大，則被不可逆地斷開，而有磁滯損失變高之傾向。因此，作為降低磁滯損失之方法，更佳為具剛直性的部位具有比利用物理交聯還多的利用化學交聯的交聯之比例。The aforementioned 100% modulus and the aforementioned hysteresis loss can be adjusted, for example, by adjusting the ratio of rigidity and flexibility, or rigidity and flexibility in the molecular chain of the resin contained in the resin molded body. Degree, degree of cross-linking, etc. For example, from the viewpoint of reducing the aforementioned 100% modulus, the aforementioned resin preferably has a flexible portion (soft segment), and when the aforementioned flexible portion has a glass transition temperature, the glass transition temperature is, for example, It is 20°C or less, preferably 0°C or less, -5°C or less, -15°C or less, -25°C or less, and -35°C or less. From the viewpoint of reducing the aforementioned hysteresis loss, the aforementioned resin preferably has a portion (hard segment) having rigidity. The aforementioned rigid part (hard segment) is a part that physically or chemically cross-links the soft segment. In terms of physical cross-linking, a functional group that can form a hydrogen bond (urethane bond group) can be used. , Urea bond groups, etc.), and chemical crosslinking includes crosslinking with a crosslinking agent (polyfunctional monomer, vulcanizing agent, etc.). Chemical cross-linking can be formed reversibly. On the other hand, if the amount of deformation of physical cross-linking increases, it is irreversibly broken, and the hysteresis loss tends to increase. Therefore, as a method of reducing the hysteresis loss, it is more preferable that the portion having rigidity has a higher ratio of crosslinking by chemical crosslinking than by physical crosslinking.

前述樹脂可為聚矽氧樹脂，亦可為丙烯酸樹脂，亦可為胺基甲酸酯樹脂。其中，就前述樹脂而言，較佳為包含胺基甲酸酯樹脂。The aforementioned resin may be a silicone resin, an acrylic resin, or a urethane resin. Among them, it is preferable that the aforementioned resin contains a urethane resin.

前述胺基甲酸酯樹脂，係較佳為包含具有羥基的聚合物(A)之主劑(i)、與硬化劑(ii)的反應物。在本發明中，主劑(i)及硬化劑(ii)可各自包含直接參與硬化物形成的成分(例如，聚合物、具有硬化作用之化合物等)以外之成分，亦可為主劑(i)的組成物、硬化劑(ii)的組成物。The aforementioned urethane resin is preferably a reaction product containing the main agent (i) of the polymer (A) having a hydroxyl group and the hardener (ii). In the present invention, the main agent (i) and the hardening agent (ii) may each contain components other than those directly involved in the formation of hardened products (for example, polymers, compounds with hardening effect, etc.), or the main agent (i) ) Composition, hardener (ii) composition.

前述具有羥基的聚合物(A)，係較佳為多元醇(a)或多元醇(a)及聚異氰酸酯(b)的反應物。The aforementioned polymer (A) having a hydroxyl group is preferably a polyol (a) or a reaction product of a polyol (a) and a polyisocyanate (b).

前述多元醇(a)係包含在25℃下為液狀的聚碳酸酯多元醇(a1)(以下，有時稱為「液狀聚碳酸酯多元醇(a1)」。)。The aforementioned polyol (a) contains a polycarbonate polyol (a1) that is liquid at 25°C (hereinafter, it may be referred to as "liquid polycarbonate polyol (a1)").

就前述液狀聚碳酸酯多元醇(a1)而言，可列舉例如，碳酸酯與多價醇的酯化反應物、多價醇與光氣的反應物之中，在25℃下為液狀者。The aforementioned liquid polycarbonate polyol (a1) includes, for example, an esterification reaction product of a carbonate ester and a polyvalent alcohol, and a reaction product of a polyvalent alcohol and phosgene, which is liquid at 25°C. By.

就前述碳酸酯而言，可使用1種或2種以上，可列舉例如脂肪族碳酸酯、脂環式碳酸酯(以下，有時將包含脂環結構稱為「脂環式」。)、芳香族碳酸酯(以下，有時將包含芳香族結構統稱為「芳香族」。)。就脂肪族碳酸酯而言，可列舉碳酸二甲酯、碳酸二乙酯、碳酸乙甲酯、碳酸二正丁酯、碳酸二異丁酯、碳酸乙基正丁酯、碳酸乙基異丁酯等之飽和脂肪族碳酸酯；碳酸伸乙酯、碳酸三亞甲酯、碳酸四亞甲酯、碳酸1,2-伸丙酯、碳酸1,2-伸丁酯、碳酸1,3-伸丁酯、碳酸2,3-伸丁酯、碳酸1,2-伸戊酯、碳酸1,3-伸戊酯、碳酸1,4-伸戊酯、碳酸1,5-伸戊酯、碳酸2,3-伸戊酯及碳酸2,4-伸戊酯等之不飽和脂肪族碳酸酯等。就芳香族碳酸酯而言，可列舉碳酸二苯酯、碳酸二苄酯等。Regarding the aforementioned carbonates, one kind or two or more kinds can be used, and examples include aliphatic carbonates, alicyclic carbonates (hereinafter, an alicyclic structure may be referred to as "alicyclic"), aromatics Carbonic acid ester (Hereinafter, the aromatic structure may be collectively referred to as "aromatic"). As for aliphatic carbonates, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, ethyl n-butyl carbonate, ethyl isobutyl carbonate can be cited Saturated aliphatic carbonate; ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate , 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3 carbonate -Unsaturated aliphatic carbonates such as pentylene and 2,4-pentylene carbonate. Examples of aromatic carbonates include diphenyl carbonate, dibenzyl carbonate, and the like.

就前述多價醇而言，可使用1種或2種以上，可列舉例如，乙二醇、丙二醇、丁二醇、戊二醇、3-甲基-1,5-戊二醇、己二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇、聚乙二醇、聚丙二醇等之直鏈狀或支鏈狀的二醇；1,4-環己烷二甲醇、氫化雙酚A等之脂環式二醇；三羥甲基甲烷、三羥甲基丙烷、二三羥甲基丙烷、新戊四醇、二新戊四醇等之3官能以上的多元醇等。Regarding the aforementioned polyvalent alcohols, one kind or two or more kinds can be used, for example, ethylene glycol, propylene glycol, butylene glycol, pentanediol, 3-methyl-1,5-pentanediol, and hexamethylene glycol. Alcohol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol and other linear or branched diols; 1,4-cyclohexanedimethanol, hydrogenated bis Alicyclic diols such as phenol A; trimethylolmethane, trimethylolpropane, ditrimethylolpropane, neopentylerythritol, dineopentylerythritol and other trifunctional or higher polyols, etc.

前述液狀聚碳酸酯多元醇只要在25℃下為液狀即可，亦可為非晶性或結晶性聚碳酸酯多元醇，較佳為非晶性聚碳酸酯多元醇。前述液狀聚碳酸酯多元醇所含之羥基的數量較佳為2。The aforementioned liquid polycarbonate polyol may be liquid at 25°C, and may be an amorphous or crystalline polycarbonate polyol, and is preferably an amorphous polycarbonate polyol. The number of hydroxyl groups contained in the aforementioned liquid polycarbonate polyol is preferably two.

前述液狀聚碳酸酯多元醇的黏度，係在室溫(25℃)下較佳為10,000mPa･s以下，更佳為7,000mPa･s以下，進一步較佳為5,000mPa･s以下，例如為100mPa･s以上、較佳為500mPa･s以上。The viscosity of the aforementioned liquid polycarbonate polyol is preferably 10,000 mPa･s or less at room temperature (25°C), more preferably 7,000 mPa･s or less, and still more preferably 5,000 mPa･s or less, for example 100mPa･s or more, preferably 500mPa･s or more.

前述液狀聚碳酸酯多元醇的數量平均分子量，係較佳為超過500，更佳為600以上，進一步較佳為700以上，較佳為小於2,000，更佳為1,800以下，進一步較佳為1,500以下。The number average molecular weight of the aforementioned liquid polycarbonate polyol is preferably more than 500, more preferably 600 or more, still more preferably 700 or more, preferably less than 2,000, more preferably 1,800 or less, and still more preferably 1,500 the following.

本說明書中，數量平均分子量、重量平均分子量係表示利用凝膠滲透層析術(GPC)而將聚苯乙烯用作標準試料所得之換算值。In this specification, the number-average molecular weight and the weight-average molecular weight refer to conversion values obtained by using gel permeation chromatography (GPC) and using polystyrene as a standard sample.

前述液狀聚碳酸酯多元醇的玻璃轉移溫度，係較佳為-100℃以上，更佳為-90℃以上，進一步較佳為-80℃以上，特佳為-75℃以上，較佳為-5℃以下，更佳為-15℃以下，進一步較佳為-25℃以下，特佳為-35℃以下。The glass transition temperature of the aforementioned liquid polycarbonate polyol is preferably -100°C or higher, more preferably -90°C or higher, still more preferably -80°C or higher, particularly preferably -75°C or higher, and more preferably -5°C or lower, more preferably -15°C or lower, still more preferably -25°C or lower, particularly preferably -35°C or lower.

前述液狀聚碳酸酯多元醇的含有率，係前述多元醇(a)中較佳為70質量%以上，更佳為80質量%以上，進一步較佳為90質量%以上，上限為100質量%。The content of the liquid polycarbonate polyol is preferably 70% by mass or more in the polyol (a), more preferably 80% by mass or more, still more preferably 90% by mass or more, and the upper limit is 100% by mass .

前述多元醇(a)係除了在前述25℃下為液狀之聚碳酸酯多元醇(a1)以外，亦可包含其他多元醇(a2)。就前述其他多元醇(a2)而言，可列舉例如，聚酯多元醇、聚醚多元醇、前述液狀聚碳酸酯多元醇(a1)以外之聚碳酸酯多元醇、低分子量多元醇等。The aforementioned polyol (a) may contain other polyols (a2) in addition to the polycarbonate polyol (a1) which is liquid at the aforementioned 25°C. Examples of the aforementioned other polyol (a2) include polyester polyols, polyether polyols, polycarbonate polyols other than the aforementioned liquid polycarbonate polyol (a1), and low molecular weight polyols.

就前述聚酯多元醇而言，可使用1種或2種以上，可列舉例如，將低分子量的多元醇、與多羧酸進行反應而得之聚酯多元醇；將ε-己內酯等之環狀酯化合物進行開環聚合反應而得之聚酯多元醇；將該等共聚合而得之聚酯多元醇等。Regarding the aforementioned polyester polyol, one kind or two or more kinds can be used, for example, polyester polyols obtained by reacting low-molecular-weight polyols and polycarboxylic acids; ε-caprolactone, etc. Polyester polyol obtained by the ring-opening polymerization reaction of the cyclic ester compound; polyester polyol obtained by copolymerizing the same.

就用於製造前述聚酯多元醇之低分子量的多元醇而言，可使用1種或2種以上，可列舉例如，乙二醇、二乙二醇、三乙二醇、四乙二醇、1,2-丙二醇、1,3-丙二醇、二丙二醇、三丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、新戊二醇、1,5-己二醇、1,6-己二醇、2,5-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,11-十一烷二醇、1,12-十二烷二醇、2-甲基-1,3-丙二醇、新戊二醇、2-丁基-2-乙基-1,3-丙二醇、3-甲基-1,5-戊二醇、2-乙基-1,3-己二醇、2-甲基-1,8-辛二醇、甘油、三羥甲基丙烷、二三羥甲基丙烷、三羥甲基丙烷、新戊四醇等之分子量為50以上300以下之脂肪族多元醇；環己烷二甲醇、氫化雙酚A等之具有脂環式結構的多元醇；雙酚A及雙酚F等之具有芳香族結構的多元醇等。Regarding the low molecular weight polyols used in the production of the aforementioned polyester polyols, one kind or two or more kinds can be used, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octane Glycol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, Neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl Aliphatic polyols with a molecular weight of 50 to 300, such as trimethylolpropane, ditrimethylolpropane, trimethylolpropane, neopentyl erythritol, etc.; Polyols with alicyclic structures such as hexanedimethanol and hydrogenated bisphenol A; polyols with aromatic structures such as bisphenol A and bisphenol F, etc.

就前述多羧酸而言，可使用1種或2種以上，可列舉例如，琥珀酸、己二酸、癸二酸、十二烷二羧酸等之脂肪族多羧酸；1,4-環己烷二羧酸、環己烷三羧酸等之脂環式多羧酸；對酞酸、異酞酸、酞酸、萘二羧酸等之芳香族多羧酸；該等的酸酐或酯化物等。Regarding the aforementioned polycarboxylic acid, one kind or two or more kinds can be used, for example, aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, dodecane dicarboxylic acid, etc.; 1,4- Alicyclic polycarboxylic acids such as cyclohexanedicarboxylic acid and cyclohexanetricarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, etc.; these acid anhydrides or Ester and so on.

就前述聚醚多元醇而言，可使用1種或2種以上，可列舉例如，將具有2個以上活性氫原子之化合物的1種或2種以上作為起始劑並使環氧烷進行加成聚合之化合物等。就前述具有2個以上活性氫原子之化合物而言，可列舉例如，丙二醇、三亞甲基二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、甘油、二甘油、三羥甲基乙烷、三羥甲基丙烷、水、己三醇等。又，就前述環氧烷而言，可列舉例如，環氧丙烷、環氧丁烷、苯環氧乙烷、表氯醇、四氫呋喃等。Regarding the aforementioned polyether polyol, one kind or two or more kinds can be used. For example, one kind or two or more kinds of compounds having two or more active hydrogen atoms are used as the initiator and alkylene oxide is added. Into polymeric compounds, etc. As for the aforementioned compound having two or more active hydrogen atoms, for example, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, Neopentyl glycol, glycerin, diglycerin, trimethylolethane, trimethylolpropane, water, hexanetriol, etc. Moreover, as for the aforementioned alkylene oxide, for example, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and the like can be cited.

就前述液狀聚碳酸酯多元醇(a1)以外之聚碳酸酯多元醇而言，可列舉例如，25℃下固體狀的聚碳酸酯多元醇等。Examples of polycarbonate polyols other than the aforementioned liquid polycarbonate polyol (a1) include solid polycarbonate polyols at 25°C and the like.

前述聚酯多元醇、前述聚醚多元醇、前述聚碳酸酯多元醇(a1)以外之聚碳酸酯多元醇的數量平均分子量，係較佳為超過300，更佳為500以上，進一步較佳為700以上，較佳為10,000以下，更佳為5,000以下，進一步較佳為4,000以下。The number average molecular weight of the polyester polyol, the polyether polyol, and the polycarbonate polyol other than the polycarbonate polyol (a1) is preferably more than 300, more preferably 500 or more, and still more preferably 700 or more, preferably 10,000 or less, more preferably 5,000 or less, still more preferably 4,000 or less.

就前述低分子量多元醇而言，可使用1種或2種以上，可列舉例如，乙二醇、二乙二醇、三乙二醇、四乙二醇、1,2-丙二醇、1,3-丙二醇、二丙二醇、三丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、新戊二醇、1,5-己二醇、1,6-己二醇、2,5-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,11-十一烷二醇、1,12-十二烷二醇、2-甲基-1,3-丙二醇、新戊二醇、2-丁基-2-乙基-1,3-丙二醇、3-甲基-1,5-戊二醇、2-乙基-1,3-己二醇、2-甲基-1,8-辛二醇、甘油、三羥甲基丙烷、二三羥甲基丙烷、三羥甲基丙烷、新戊四醇等的分子量為50以上300以下之脂肪族多元醇；環己烷二甲醇、氫化雙酚A等之具有脂環式結構的多元醇；雙酚A及雙酚F等之具有芳香族結構的多元醇等。Regarding the aforementioned low-molecular-weight polyols, one kind or two or more kinds can be used, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3 -Propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, new Pentylene glycol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonane Alcohol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl -2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol , Glycerol, trimethylolpropane, ditrimethylolpropane, trimethylolpropane, neopentylerythritol and other aliphatic polyols with a molecular weight of 50 to 300; cyclohexane dimethanol, hydrogenated bisphenol A Polyols with alicyclic structures such as bisphenol A and bisphenol F, etc.; polyols with aromatic structure such as bisphenol A and bisphenol F.

前述其他多元醇的含有率，係前述多元醇(a)中例如為30質量%以下、20質量%以下、10質量%以下，下限為0質量%。The content rate of the aforementioned other polyol is, for example, 30% by mass or less, 20% by mass or less, and 10% by mass or less in the aforementioned polyol (a), and the lower limit is 0% by mass.

就前述聚異氰酸酯(b)而言，可使用1種或2種以上，可列舉脂肪族聚異氰酸酯、脂環式聚異氰酸酯、芳香族聚異氰酸酯等，較佳為使用脂肪族或脂環式聚異氰酸酯。就前述脂肪族或脂環式聚異氰酸酯而言，可使用1種或2種以上，可使用例如，四亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯、十二亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、1,3-伸環戊基二異氰酸酯、1,3-伸環己基二異氰酸酯、1,4-伸環己基二異氰酸酯、1,3-二(異氰酸酯甲基)環己烷、1,4-二(異氰酸酯甲基)環己烷、離胺酸二異氰酸酯、異佛酮二異氰酸酯、4,4’-二環己基甲烷二異氰酸酯、2,4’-二環己基甲烷二異氰酸酯、2,2’-二環己基甲烷二異氰酸酯、3,3’-二甲基-4,4’-二環己基甲烷二異氰酸酯等。又，可使用前述脂肪族或脂環式聚異氰酸酯的脲甲酸酯改質體、異三聚氰酸酯改質體等。在該等之中，較佳為脂肪族或脂環式聚異氰酸酯的脲甲酸酯改質體或異三聚氰酸酯改質體，更佳為脂肪族或脂環式聚異氰酸酯的異三聚氰酸酯改質體，進一步較佳為脂肪族聚異氰酸酯的異三聚氰酸酯改質體。Regarding the aforementioned polyisocyanate (b), one kind or two or more kinds can be used, including aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, etc., preferably aliphatic or alicyclic polyisocyanate is used . Regarding the aforementioned aliphatic or alicyclic polyisocyanate, one kind or two or more kinds can be used. For example, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate can be used. Isocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentyl diisocyanate, 1,3-cyclohexyl diisocyanate, 1,4-cyclohexyl diisocyanate, 1,3-bis(isocyanate Methyl)cyclohexane, 1,4-bis(isocyanate methyl)cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'- Dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, etc. In addition, an allophanate modified body of the aforementioned aliphatic or alicyclic polyisocyanate, an isocyanurate modified body, etc. can be used. Among them, the allophanate modified body or isocyanurate modified body of aliphatic or alicyclic polyisocyanate is preferred, and the isotricyanurate modified body of aliphatic or alicyclic polyisocyanate is more preferred. The polycyanate modified body is more preferably an isocyanurate modified body of aliphatic polyisocyanate.

前述聚異氰酸酯(b)所含之異氰酸酯基、與前述多元醇(a)所含之羥基的莫耳比(NCO/OH)，係較佳為0.8以上，更佳為0.9以上，進一步較佳為1.0以上，較佳為1.3以下，更佳為1.2以下，進一步較佳為1.1以下。The molar ratio (NCO/OH) of the isocyanate group contained in the polyisocyanate (b) to the hydroxyl group contained in the polyol (a) is preferably 0.8 or more, more preferably 0.9 or more, and still more preferably 1.0 or more, preferably 1.3 or less, more preferably 1.2 or less, and still more preferably 1.1 or less.

前述聚合物(A)可直接為前述多元醇(a)，亦可藉由使前述多元醇(a)及前述聚異氰酸酯(b)反應而製造。The polymer (A) may be directly the polyol (a), or it may be produced by reacting the polyol (a) and the polyisocyanate (b).

使前述多元醇(a)及前述聚異氰酸酯(b)反應時，亦可因應需要而使胺基甲酸酯化觸媒共存。就前述胺基甲酸酯化觸媒而言，可使用1種或2種以上，可列舉例如，三乙胺、三丁胺、苄基二丁胺、三伸乙二胺、N-甲基

Figure 109113221-A0304-12-01
啉等之含氮化合物；或者四丁氧基鈦、二丁基氧化錫、二月桂酸二丁基錫、2-乙基己酸錫、環烷酸鋅、環烷酸鈷、2-乙基己酸鋅、硫乙醇酸鉬、乙酸鉀、硬脂酸鋅、辛酸錫、二月桂酸二丁基錫、二新癸酸二辛基錫等之有機金屬化合物；或者氯化鐵、氯化鋅等之無機化合物等。When the polyol (a) and the polyisocyanate (b) are reacted, a urethane catalyst may coexist as needed. Regarding the aforementioned carbamate catalyst, one or more than two can be used, for example, triethylamine, tributylamine, benzyldibutylamine, triethylenediamine, N-methyl
Figure 109113221-A0304-12-01
Nitrogen-containing compounds such as morphine; or titanium tetrabutoxide, dibutyltin oxide, dibutyltin dilaurate, tin 2-ethylhexanoate, zinc naphthenate, cobalt naphthenate, 2-ethylhexanoic acid Organometallic compounds such as zinc, molybdenum thioglycolate, potassium acetate, zinc stearate, tin octoate, dibutyltin dilaurate, dioctyltin dineodecanoate, etc.; or inorganic compounds such as iron chloride and zinc chloride Wait.

前述反應時，亦可使反應溶劑共存。就前述反應溶劑而言，可使用1種或2種以上，可列舉例如，甲苯、二甲苯等之芳香族烴溶劑；丙酮、甲基乙基酮、環己酮、乙醯丙酮等之酮溶劑；四氫呋喃、二

Figure 109113221-A0304-12-02
烷等之醚溶劑；乙酸乙酯、乙酸丁酯等之酯溶劑；乙腈等之腈溶劑；二甲基甲醯胺、N-甲基吡咯啶酮等之醯胺溶劑等。During the aforementioned reaction, a reaction solvent may coexist. Regarding the aforementioned reaction solvent, one or more than two types can be used, for example, aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and acetone ; Tetrahydrofuran, two
Figure 109113221-A0304-12-02
Ether solvents such as alkane; ester solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone.

前述反應時，反應溫度係例如可在50~90℃進行，反應時間係例如可在2~24小時進行。反應壓力可為常壓、加壓、減壓中任一者。反應氣體環境可為氮、氬等之惰性氣體環境，亦可為乾燥空氣環境、密閉條件等之未混入水分的條件。In the aforementioned reaction, the reaction temperature can be carried out at 50 to 90°C, and the reaction time can be carried out at 2 to 24 hours, for example. The reaction pressure may be any of normal pressure, increased pressure, and reduced pressure. The reactive gas environment can be an inert gas environment such as nitrogen, argon, etc., or can be a dry air environment, airtight conditions, and other conditions where no moisture is mixed in.

前述聚合物(A)的羥基當量，係較佳為400g/eq.以上，更佳為450g/eq.以上，較佳為4000g/eq.以下，更佳為3000g/eq.以下。The hydroxyl equivalent of the aforementioned polymer (A) is preferably 400 g/eq. or more, more preferably 450 g/eq. or more, preferably 4000 g/eq. or less, and more preferably 3000 g/eq. or less.

前述硬化劑(ii)係較佳為包含聚異氰酸酯化合物(d)。前述聚異氰酸酯化合物(d)具有2個以上異氰酸酯基。就前述聚異氰酸酯化合物(d)而言，可使用1種或2種以上，例如，就具有2個異氰酸酯基之二異氰酸酯化合物而言，可列舉環己烷二異氰酸酯、二環己基甲烷二異氰酸酯、異佛酮二異氰酸酯等之具有脂環式結構的二異氰酸酯；六亞甲基二異氰酸酯、離胺酸二異氰酸酯、伸茬基二異氰酸酯、四甲基伸茬基二異氰酸酯等之脂肪族二異氰酸酯等；就具有3個以上異氰酸酯基之聚異氰酸酯化合物而言，可列舉二異氰酸酯的異三聚氰酸酯體、二異氰酸酯的三羥甲基丙烷加合物等，較佳為二異氰酸酯的異三聚氰酸酯體。就前述二異氰酸酯而言，可列舉六亞甲基二異氰酸酯等之脂肪族二異氰酸酯、異佛酮二異氰酸酯等之脂環式二異氰酸酯等。The aforementioned curing agent (ii) preferably contains a polyisocyanate compound (d). The aforementioned polyisocyanate compound (d) has two or more isocyanate groups. Regarding the aforementioned polyisocyanate compound (d), one kind or two or more kinds can be used. For example, as for the diisocyanate compound having two isocyanate groups, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, Diisocyanates with alicyclic structure such as isophorone diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, stubborn diisocyanate, tetramethyl stubborn diisocyanate, etc. ; For the polyisocyanate compound having 3 or more isocyanate groups, the isocyanurate body of diisocyanate, the trimethylolpropane adduct of diisocyanate, etc. are mentioned, and the isotrimerization of diisocyanate is preferred Cyanate ester. The aforementioned diisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate, and alicyclic diisocyanates such as isophorone diisocyanate.

其中，前述聚異氰酸酯化合物(d)係較佳為包含具有3個以上異氰酸酯基之聚異氰酸酯化合物。前述具有3個以上異氰酸酯基之聚異氰酸酯化合物的含有率，係前述聚異氰酸酯化合物(d)中較佳為50質量%以上，更佳為80質量%以上，進一步較佳為90質量%以上，上限為100質量%。Among them, the aforementioned polyisocyanate compound (d) preferably contains a polyisocyanate compound having three or more isocyanate groups. The content of the polyisocyanate compound having 3 or more isocyanate groups is preferably 50% by mass or more in the polyisocyanate compound (d), more preferably 80% by mass or more, and still more preferably 90% by mass or more, the upper limit It is 100% by mass.

前述硬化劑(ii)的含有率，係前述主劑(i)與前述硬化劑(ii)的合計中小於50質量%，較佳為40質量%以下，更佳為30質量%以下，進一步較佳為20質量%以下，且下限係例如為0.1質量%。The content of the curing agent (ii) is less than 50% by mass in the total of the main agent (i) and the curing agent (ii), preferably 40% by mass or less, more preferably 30% by mass or less, and more It is preferably 20% by mass or less, and the lower limit is, for example, 0.1% by mass.

前述主劑(i)所含之聚合物(A)的羥基、與前述硬化劑(ii)所含之聚異氰酸酯化合物(d)的異氰酸酯基的莫耳比(NCO/OH)，係較佳為0.8以上，更佳為0.9以上，較佳為1.5以下，更佳為1.2以下。The molar ratio (NCO/OH) of the hydroxyl group of the polymer (A) contained in the main agent (i) and the isocyanate group of the polyisocyanate compound (d) contained in the curing agent (ii) is preferably 0.8 or more, more preferably 0.9 or more, preferably 1.5 or less, more preferably 1.2 or less.

前述胺基甲酸酯樹脂的含有率，係前述樹脂成形體所含之樹脂中較佳為50質量%以上，更佳為80質量%以上，進一步較佳為90質量%以上，上限為100質量%。The content of the urethane resin is preferably 50% by mass or more in the resin contained in the resin molded body, more preferably 80% by mass or more, still more preferably 90% by mass or more, and the upper limit is 100% by mass %.

前述樹脂的含有率，係前述樹脂成形體中較佳為50質量%以上，更佳為80質量%以上，進一步較佳為90質量%以上，上限為100質量%。The content of the resin is preferably 50% by mass or more in the resin molded body, more preferably 80% by mass or more, still more preferably 90% by mass or more, and the upper limit is 100% by mass.

前述動摩擦力係例如可藉由使用滑性賦予劑而達成。前述滑性賦予劑係較佳為與前述樹脂不相溶者。因此，前述滑性賦予劑與前述樹脂的溶解度參數之差，係較佳為2(cal/cm3 )0.5 以上，更佳為2.5(cal/cm3 )0.5 以上，進一步較佳為3(cal/cm3 )0.5 以上，且上限係例如可為10(cal/cm3 )0.5 以下、8(cal/cm3 )0.5 以下。The aforementioned dynamic friction system can be achieved, for example, by using a slippery imparting agent. The aforementioned slippery imparting agent is preferably one that is incompatible with the aforementioned resin. Therefore, the difference between the solubility parameter of the aforementioned slippery imparting agent and the aforementioned resin is preferably 2 (cal/cm 3 ) 0.5 or more, more preferably 2.5 (cal/cm 3 ) 0.5 or more, and still more preferably 3 (cal/cm 3) 0.5 or more. /cm 3 ) 0.5 or more, and the upper limit may be, for example, 10 (cal/cm 3 ) 0.5 or less and 8 (cal/cm 3 ) 0.5 or less.

前述溶解度參數，係可根據樹脂及滑性賦予劑的化學結構式，使用Fedors的式而計算(Polymer Engineering and Science，1974，col.14，No.12)。The aforementioned solubility parameter can be calculated based on the chemical structural formula of the resin and the slippery imparting agent using Fedors' formula (Polymer Engineering and Science, 1974, col. 14, No. 12).

包含胺基甲酸酯樹脂作為前述樹脂之情形，就前述滑性賦予剤而言，較佳為包含下述式(1)所示之化合物(B)。When a urethane resin is included as the aforementioned resin, it is preferable to include the compound (B) represented by the following formula (1) in terms of the aforementioned slippery imparting agent.

Figure 02_image001
[式(1)中，R1 、R2 各自獨立地表示甲基或羥基。n表示1~3,000之整數。]
Figure 02_image001
[In formula (1), R 1 and R 2 each independently represent a methyl group or a hydroxyl group. n represents an integer from 1 to 3,000. ]

前述滑性賦予劑(iii)只要包含在前述胺基甲酸酯樹脂組成物即可，前述主劑(i)及前述硬化劑(ii)的混合順序沒有特別限定。The said slippery imparting agent (iii) should just be contained in the said urethane resin composition, and the mixing order of the said main agent (i) and the said hardening agent (ii) is not specifically limited.

式(1)中，R1 、R2 從耐擦傷性之觀點來看，較佳為甲基。n較佳為1~3,000，更佳為5~2,500，進一步較佳為6~2,200。In the formula (1), R 1 and R 2 are preferably methyl groups from the viewpoint of scratch resistance. n is preferably 1 to 3,000, more preferably 5 to 2,500, and still more preferably 6 to 2,200.

前述化合物(B)的分子量，係例如為500以上，更佳為1,000以上，進一步較佳為5,000以上，較佳為150,000以下，更佳為120,000以下，進一步較佳為110,000以下。The molecular weight of the aforementioned compound (B) is, for example, 500 or more, more preferably 1,000 or more, still more preferably 5,000 or more, preferably 150,000 or less, more preferably 120,000 or less, and still more preferably 110,000 or less.

前述化合物(B)的分子量係可基於前述化合物(B)在25℃下的動黏度，利用A.J.Barry的式而求出。The molecular weight of the compound (B) can be calculated based on the kinematic viscosity of the compound (B) at 25° C. using the formula of A.J. Barry.

前述化合物(B)可直接與前述主劑(i)及前述硬化劑(ii)混合，亦可預先分散於水等之分散介質後進行混合。The compound (B) may be directly mixed with the main agent (i) and the curing agent (ii), or may be dispersed in a dispersion medium such as water before mixing.

前述化合物(B)的含有率，係相對於前述主劑(i)及前述硬化劑(ii)的合計100質量份，而較佳為0.1質量份以上，更佳為0.2質量份以上，進一步較佳為0.5質量份以上，較佳為10質量份以下，更佳為5質量份以下，進一步較佳為3質量份以下。The content of the aforementioned compound (B) is relative to the total of 100 parts by mass of the aforementioned main agent (i) and aforementioned curing agent (ii), and is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and furthermore It is preferably 0.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less.

前述樹脂成形體，係可使用包含前述樹脂(或前述樹脂前驅物)、與前述滑性賦予劑之樹脂組成物而形成。包含胺基甲酸酯樹脂作為前述樹脂之情形，前述樹脂組成物係較佳為包含前述主劑(i)及前述硬化劑(ii)作為前述樹脂前驅物。The aforementioned resin molded body can be formed using a resin composition containing the aforementioned resin (or the aforementioned resin precursor) and the aforementioned slippery imparting agent. When a urethane resin is included as the resin, the resin composition preferably includes the main agent (i) and the hardener (ii) as the resin precursor.

前述樹脂組成物亦可包含前述有機溶劑(C)。就前述有機溶劑(C)而言，可使用1種或2種以上，可列舉例如，甲苯、二甲苯等之芳香族烴溶劑；丙酮、甲基乙基酮、環己酮、乙醯丙酮等之酮溶劑；四氫呋喃、二

Figure 109113221-A0304-12-02
烷等之醚溶劑；乙酸乙酯、乙酸丁酯等之酯溶劑；乙腈等之腈溶劑；二甲基甲醯胺、N-甲基吡咯啶酮等之醯胺溶劑等。The aforementioned resin composition may also contain the aforementioned organic solvent (C). Regarding the aforementioned organic solvent (C), one kind or two or more kinds can be used, for example, aromatic hydrocarbon solvents such as toluene and xylene; acetone, methyl ethyl ketone, cyclohexanone, acetone, etc. Ketone solvent; tetrahydrofuran, two
Figure 109113221-A0304-12-02
Ether solvents such as alkane; ester solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone.

前述有機溶劑(C)的含有率，係前述樹脂組成物中較佳為30質量%以上，更佳為40質量%以上，進一步較佳為50質量%以上，較佳為80質量%以下，更佳為70質量%以下，進一步較佳為65質量%以下。The content of the organic solvent (C) is preferably 30% by mass or more in the resin composition, more preferably 40% by mass or more, still more preferably 50% by mass or more, preferably 80% by mass or less, and more It is preferably 70% by mass or less, and more preferably 65% by mass or less.

前述樹脂組成物亦可包含其他添加劑(D)。就前述其他添加劑(D)而言，可列舉黏著賦予劑、調平劑、觸媒、塑化劑、安定劑、填充材、顏料、染料、阻燃劑等。The aforementioned resin composition may also contain other additives (D). Examples of the aforementioned other additives (D) include adhesion-imparting agents, leveling agents, catalysts, plasticizers, stabilizers, fillers, pigments, dyes, flame retardants, and the like.

包含前述其他添加劑(D)之情形，其含有率係前述樹脂組成物的全部量中，例如為30質量%以下、10質量%以下、5質量%以下，下限為0質量%。When the other additive (D) is included, the content is, for example, 30% by mass or less, 10% by mass or less, and 5% by mass or less in the total amount of the resin composition, and the lower limit is 0% by mass.

具有基材、與前述樹脂成形體之積層體，亦包含於本發明之技術範圍內。就前述基材而言，沒有特別限定，可使用：木材；聚酯樹脂、環氧樹脂、聚醯胺樹脂、丙烯酸樹脂、聚烯烴樹脂、聚碳酸酯樹脂、聚胺基甲酸酯樹脂、ABS樹脂、聚氯乙烯樹脂、聚苯乙烯樹脂、酚醛樹脂、三聚氰胺樹脂、尿素樹脂、醇酸樹脂等之合成或天然樹脂；鋁、鐵、銅、鋅、鐵合金、鋁合金、銅合金、鋅合金等之金屬；玻璃；陶瓷等之基材。A laminate having a base material and the aforementioned resin molded body is also included in the technical scope of the present invention. As for the aforementioned substrate, there is no particular limitation, and it can be used: wood; polyester resin, epoxy resin, polyamide resin, acrylic resin, polyolefin resin, polycarbonate resin, polyurethane resin, ABS Synthetic or natural resins such as resin, polyvinyl chloride resin, polystyrene resin, phenolic resin, melamine resin, urea resin, alkyd resin, etc.; aluminum, iron, copper, zinc, iron alloy, aluminum alloy, copper alloy, zinc alloy, etc. The metal; glass; ceramics and other substrates.

前述成形體的形狀沒有特別限定，只要為將前述樹脂組成物作成薄膜狀、板狀、各種的三維形狀者即可。前述成形體之成形方法沒有特別限定，可採用射出成形、擠出成形、中空成形、熱成形、吹塑成形等之成形法。又，前述成形體可為藉由將前述樹脂組成物塗敷於物品並使其硬化而形成者(硬化塗膜)。就將前述樹脂組成物塗敷於物品之方法而言，可適當採用浸漬塗布法、旋轉塗布法、流動塗布法、噴灑塗布法、輥塗法、照相凹版輥塗法、氣刀塗布法、刮板塗布法、線刀塗布法、刮刀塗布法、逆塗法、轉移輥塗法、微凹版塗布法、吻合式塗布法、澆鑄塗布法、縫孔(slot orifice)塗布法、壓延塗布法、模具塗布法等之方法。The shape of the molded body is not particularly limited, as long as the resin composition is formed into a film shape, a plate shape, or various three-dimensional shapes. The molding method of the aforementioned molded body is not particularly limited, and molding methods such as injection molding, extrusion molding, hollow molding, thermoforming, and blow molding can be used. In addition, the molded body may be formed by applying the resin composition to an article and curing it (cured coating film). As for the method of applying the aforementioned resin composition to the article, dip coating, spin coating, flow coating, spray coating, roll coating, gravure roll coating, air knife coating, and doctor blade coating methods can be suitably used. Plate coating method, wire knife coating method, knife coating method, reverse coating method, transfer roll coating method, microgravure coating method, kiss coating method, casting coating method, slot orifice coating method, calender coating method, mold Coating method and other methods.

前述樹脂成形體及前述積層體可適宜地使用於例如汽車、汽車零件、家電製品、行動電話、工業用品、醫療用品、光學構件、機器人用品、包裝材料、OA設備、運動用品等之物品。 [實施例]The aforementioned resin molded body and the aforementioned laminate can be suitably used in articles such as automobiles, automobile parts, home appliances, mobile phones, industrial products, medical products, optical components, robotics products, packaging materials, OA equipment, sports products, and the like. [Example]

以下，列舉實施例而更具體地說明本發明，但本發明並不受下述實施例限制，當然亦可在能夠符合前、後述的宗旨之範圍內加以適當地變更並實施，該等皆包含在本發明之技術範圍內。Hereinafter, the present invention will be explained in more detail by enumerating examples. However, the present invention is not limited by the following examples. Of course, it can also be appropriately modified and implemented within the scope that can conform to the purpose of the foregoing and the following. Within the technical scope of the present invention.

[調製例1] 在具備溫度計、氮氣導入管、攪拌器之經氮置換的容器中，加入甲基乙基酮100質量份、聚碳酸酯二元醇(DURANOL T-5652、旭化成股份有限公司製)100質量份並進行攪拌。接著，加入六亞甲基二異氰酸酯的異三聚氰酸酯體(BURNOCK DN-902S)8質量份、維沙狄克酸二辛基錫(dioctyltin versatate)0.01質量份。在留意放熱的同時使內溫上升至60℃，然後，在保持溫度的同時攪拌3小時，得到包含羥基的當量重量為1954之在分子末端具有羥基的預聚物(A-1)之主劑(i-1)。[Modulation example 1] Add 100 parts by mass of methyl ethyl ketone and 100 parts by mass of polycarbonate diol (DURANOL T-5652, manufactured by Asahi Kasei Co., Ltd.) into a nitrogen-replaced container equipped with a thermometer, a nitrogen introduction tube, and a stirrer. Stir. Next, 8 parts by mass of isocyanurate body (BURNOCK DN-902S) of hexamethylene diisocyanate and 0.01 parts by mass of dioctyltin versatate were added. While paying attention to the exotherm, the internal temperature was raised to 60°C, and then the temperature was maintained while stirring for 3 hours to obtain the main agent of the prepolymer (A-1) containing a hydroxyl group with an equivalent weight of 1954 and having a hydroxyl group at the end of the molecule. (i-1).

[調製例2~8] 除了如表1所述變更多元醇的種類及量、聚異氰酸酯的種類及量以外，係與調製例1同樣地進行，而得到包含如表1所示之羥基當量重量的預聚物(A-2)~(A-8)之主劑(i-2)~(i-9)。[Modulation example 2~8] Except that the type and amount of polyol and the type and amount of polyisocyanate were changed as described in Table 1, the same procedure as in Preparation Example 1 was carried out to obtain a prepolymer (A- 2)~(A-8)'s main agent (i-2)~(i-9).

[表1] 調製例 1 2 3 4 5 6 7 8 預聚物名稱 (A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) (A-8) 多元醇 PTMG2000 100 G3452 100 UH-200 100 T5652 100 50 T5651 100 90 UM-90 100 50 乙二醇 10 聚異氰酸酯 DN-902S 8 羥基當量 (g/eq.) 1954 1011 500 453 1064 624 1011 556 [Table 1] Modulation example 1 2 3 4 5 6 7 8 Prepolymer name (A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) (A-8) Polyol PTMG2000 100 G3452 100 UH-200 100 T5652 100 50 T5651 100 90 UM-90 100 50 Ethylene glycol 10 Polyisocyanate DN-902S 8 Hydroxyl equivalent (g/eq.) 1954 1011 500 453 1064 624 1011 556

表1中，PTMG2000表示聚氧四亞甲基二醇(PTMG2000、分子量2,000、三菱化學股份有限公司製)，G3452表示聚碳酸酯多元醇(G3452、數量平均分子量2,000、旭化成股份有限公司製)，UH-200表示聚碳酸酯多元醇(UH-200、平均分子量2,000、宇部興產股份有限公司製)，T5652表示聚碳酸酯多元醇(T5652、數量平均分子量2,000、旭化成股份有限公司製)，T5651表示聚碳酸酯多元醇(T5651、數量平均分子量1,000、旭化成股份有限公司製)，UM-90表示聚碳酸酯多元醇(UM-90、數量平均分子量900、宇部興產股份有限公司製)，DN-902S表示六亞甲基二異氰酸酯的異三聚氰酸酯體(BURNOCK DN-902S、DIC股份有限公司製)。In Table 1, PTMG2000 represents polyoxytetramethylene glycol (PTMG2000, molecular weight 2,000, manufactured by Mitsubishi Chemical Corporation), and G3452 represents polycarbonate polyol (G3452, number average molecular weight 2,000, manufactured by Asahi Kasei Co., Ltd.). UH-200 represents polycarbonate polyol (UH-200, average molecular weight 2,000, manufactured by Ube Industries Co., Ltd.), T5652 represents polycarbonate polyol (T5652, number average molecular weight 2,000, manufactured by Asahi Kasei Co., Ltd.), T5651 Represents polycarbonate polyol (T5651, number average molecular weight 1,000, manufactured by Asahi Kasei Co., Ltd.), UM-90 represents polycarbonate polyol (UM-90, number average molecular weight 900, manufactured by Ube Industries Co., Ltd.), DN -902S represents an isocyanurate body of hexamethylene diisocyanate (BURNOCK DN-902S, manufactured by DIC Co., Ltd.).

[實施例1] 以成為NCO/OH比=1.10之方式混合主劑(i)100質量份、硬化劑(ii)(六亞甲基二異氰酸酯的異三聚氰酸酯體(BURNOCK DN-902S)5.3質量份，進一步混合滑性賦予劑(iii)WACKER AK-1000(二甲基聚矽氧烷油)0.5質量份、調平劑(SILCLEAN 3700、BYK Japan製)1.5質量份，而得到熱硬化型胺基甲酸酯樹脂組成物(1)。[Example 1] Mix the main agent (i) 100 parts by mass and the hardener (ii) (BURNOCK DN-902S) of 5.3 parts by mass of the hardener (BURNOCK DN-902S) so that the NCO/OH ratio=1.10, Furthermore, a slippery imparting agent (iii) 0.5 parts by mass of WACKER AK-1000 (dimethyl polysiloxane oil) and 1.5 parts by mass of a leveling agent (SILCLEAN 3700, manufactured by BYK Japan) were mixed to obtain a thermosetting polyurethane Ester resin composition (1).

[實施例2~8、比較例1~5] 除了如表2或表3所示變更主劑(i)、硬化劑(ii)、滑性賦予劑(iii)以外，係與實施例1同樣地進行，得到熱硬化型胺基甲酸酯樹脂組成物(1)~(8)、比較組成物(1)~(7)。[Examples 2 to 8, Comparative Examples 1 to 5] Except that the main agent (i), curing agent (ii), and slipperiness imparting agent (iii) were changed as shown in Table 2 or Table 3, the same procedure as in Example 1 was carried out to obtain a thermosetting urethane resin Compositions (1)~(8), comparative compositions (1)~(7).

以下述方法對所得之胺基甲酸酯樹脂組成物、比較組成物進行評價。The obtained urethane resin composition and the comparative composition were evaluated by the following methods.

[100%模數與伸長度之評價方法] 藉由刮刀塗布機，將實施例及比較例所得之熱硬化型胺基甲酸酯樹脂組成物以使固體成分膜厚成為30微米之方式塗布於PET薄膜上，在70℃乾燥2分鐘，進一步在110℃乾燥2分鐘，而製作聚胺基甲酸酯樹脂薄膜。接著，將聚胺基甲酸酯樹脂薄膜切出寬5mm、長度50mm的條狀的試驗片，使用拉伸試驗機，在卡盤間距離40mm、拉伸速度10mm/秒、溫度23℃的環境下，實施拉伸試驗，將100%延伸時的應力設為100%模數，將斷裂時的伸度設為伸長度。[Evaluation method of 100% modulus and elongation] Using a knife coater, the thermosetting urethane resin composition obtained in the examples and comparative examples was coated on a PET film so that the solid content film thickness became 30 microns, and dried at 70°C for 2 minutes, and further It was dried at 110°C for 2 minutes to produce a polyurethane resin film. Next, the polyurethane resin film was cut into strip test pieces with a width of 5 mm and a length of 50 mm. Using a tensile testing machine, the distance between the chucks was 40 mm, the tensile speed was 10 mm/sec, and the temperature was 23°C. Next, a tensile test was performed, and the stress at 100% elongation was set to 100% modulus, and the elongation at break was set to elongation.

[100%伸長回復時的磁滯損失之評價方法] 使用拉伸試驗機，以卡盤間距離40mm、拉伸速度10mm/秒、溫度23℃的環境下，實施拉伸試驗，將從與上述同樣地進行而得之聚胺基甲酸酯樹脂薄膜切出之條狀試驗片進行100%延伸後，立即以拉伸速度10mm/秒恢復至卡盤間距離40mm。此時，從所施加的負載與變形量之圖表的積分值，將由試驗片在拉伸時被施予的熱量與在拉回時試驗片所放出的熱量之差所求出之熱量的損失比例設為磁滯損失。[Evaluation method of hysteresis loss at 100% elongation recovery] Using a tensile testing machine, the chuck distance is 40mm, the tensile speed is 10mm/sec, and the temperature is 23°C. The tensile test is carried out, and the polyurethane resin film is obtained from the same procedure as above. After the cut strip test piece is stretched 100%, it is restored to the distance between the chucks 40mm at a stretching speed of 10mm/sec. At this time, from the integral value of the graph of the applied load and the amount of deformation, the heat loss ratio is calculated from the difference between the heat applied to the test piece when it is stretched and the heat released by the test piece when it is pulled back Set as hysteresis loss.

[滑性之評價方法] 使用新東科學股份有限公司製表面製測定器，以負載200g、10mm不鏽鋼製球壓頭、試驗速度120cm/分鐘，測定與上述同樣地進行而得之聚胺基甲酸酯薄膜的摩擦電阻。 以下述基準評價所測定之應力。 ○：小於2kN △：2kN以上且小於1000kN ××：1000kN以上[Method of evaluating slipperiness] Using a surface measuring device manufactured by Shinto Scientific Co., Ltd., a load of 200 g, a 10 mm stainless steel ball indenter, and a test speed of 120 cm/min were used to measure the friction resistance of the polyurethane film obtained in the same manner as described above. The measured stress was evaluated based on the following criteria. ○: Less than 2kN △: 2kN or more and less than 1000kN ××: Above 1000kN

[耐溶劑性之評價方法] 確認對與上述同樣地進行而得之聚胺基甲酸酯樹脂薄膜，以滴管垂直滴下1滴MEK，且於10秒後擦掉時的外觀變化。滴落的部分膨潤，且以目視可確認之情形係評價為△，完全無法確認之情形係評價為○。[Evaluation method of solvent resistance] The appearance of the polyurethane resin film obtained in the same manner as above was confirmed when one drop of MEK was dropped vertically with a dropper and wiped off after 10 seconds. The dripping part was swollen, and when it was confirmed visually, it was evaluated as △, and when it could not be confirmed at all, it was evaluated as ○.

[鋼絲絨耐擦傷性之評價方法] 使用RUBBING TESTER(太平理化工業股份有限公司製)進行評價。 具體而言，使用鋼絲絨(日本 Steel Wool股份有限公司製、商品名BONSTAR、商品編號No.0000)作為磨耗體，將該磨耗體以負載500g之條件，往復500次摩擦前述塗膜表面。將摩擦後之塗膜表面的狀態藉由目視，而根據下述評價基準進行評價。 ○：在皮膜表面沒有產生刮痕。 ×：在皮膜表面可見條紋刮痕。[Method for evaluating scratch resistance of steel wool] RUBBING TESTER (manufactured by Taiping Chemical Industry Co., Ltd.) was used for evaluation. Specifically, steel wool (manufactured by Japan Steel Wool Co., Ltd., brand name BONSTAR, product code No. 0000) was used as the abrasion body, and the abrasion body was rubbed back and forth 500 times on the surface of the coating film under the condition of a load of 500 g. The state of the coating film surface after rubbing was visually evaluated based on the following evaluation criteria. ○: No scratches are generated on the surface of the film. ×: Streak scratches are seen on the surface of the film.

[表2] 實施例 1 2 3 4 5 6 7 8 9 組成（質量份） 主劑(ⅰ) (i-1) 100 100 100 100 (i-2) 100 (i-3) 100 (i-5) 100 100 (i-7) 100 硬化劑(ⅱ) 聚異氰酸酯 DN-902S 5.3 5.3 5.3 5.3 9.8 19.8 9.3 5.7 9.8 HDI 1.7 滑性賦予劑 (ⅲ) AK1000 0.5 0.5 0.5 0.5 0.5 0.5 AK10000 0.5 AK100000 0.5 C800 0.5 添加劑 調平劑 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 評價結果 100%M(MPa) 3.2 3.2 3.2 3.2 2.6 4.7 2.9 2.0 2.0 100%磁滯損失(%) 0.2 0.2 0.2 0.2 0.9 0.2 1.6 7.6 1.0 伸長度(%) 136 136 136 136 235 107 290 390 350 滑性 ○ ○ ○ ○ ○ ○ ○ ○ ○ 耐溶劑性 ○ ○ ○ ○ ○ ○ ○ ○ △ SW耐擦傷性500次 ○ ○ ○ ○ ○ ○ ○ ○ ○ [Table 2] Example 1 2 3 4 5 6 7 8 9 Composition (parts by mass) Main agent (ⅰ) (i-1) 100 100 100 100 (i-2) 100 (i-3) 100 (i-5) 100 100 (i-7) 100 Hardener (ⅱ) Polyisocyanate DN-902S 5.3 5.3 5.3 5.3 9.8 19.8 9.3 5.7 9.8 HDI 1.7 Slippery imparting agent (ⅲ) AK1000 0.5 0.5 0.5 0.5 0.5 0.5 AK10000 0.5 AK100000 0.5 C800 0.5 additive Leveling agent 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Evaluation results 100%M(MPa) 3.2 3.2 3.2 3.2 2.6 4.7 2.9 2.0 2.0 100% hysteresis loss (%) 0.2 0.2 0.2 0.2 0.9 0.2 1.6 7.6 1.0 Elongation (%) 136 136 136 136 235 107 290 390 350 Slippery ○ ○ ○ ○ ○ ○ ○ ○ ○ Solvent resistance ○ ○ ○ ○ ○ ○ ○ ○ △ SW scratch resistance 500 times ○ ○ ○ ○ ○ ○ ○ ○ ○

[表3] 比較例 1 2 3 4 5 6 組成(質量份) 主劑(ⅰ) (i-1) 100 100 100 (i-4) 100 (i-6) 100 (i-8) 100 硬化劑(ⅱ) 聚異氰酸酯 DN-902S 5.3 5.3 5.3 21.9 15.9 15.0 滑性賦予劑 (iii) AK1000 0.5 0.5 0.5 KF53 0.5 BYK-333 0.5 添加劑 調平劑 3.0 3.0 3.0 3.0 3.0 3.0 評價結果 100%M(MPa) 3.2 3.2 3.2 4.1 3.7 7.0 100%磁滯損失(%) 0.2 0.2 0.2 43.0 25.0 24.0 伸長度(%) 136 136 136 165 145 80 滑性 △ △ △ ○ ○ ○ 耐溶劑性 ○ ○ ○ ○ ○ ○ SW耐擦傷性500次 × × × × × × [table 3] Comparative example 1 2 3 4 5 6 Composition (parts by mass) Main agent (ⅰ) (i-1) 100 100 100 (i-4) 100 (i-6) 100 (i-8) 100 Hardener (ⅱ) Polyisocyanate DN-902S 5.3 5.3 5.3 21.9 15.9 15.0 Slippery imparting agent (iii) AK1000 0.5 0.5 0.5 KF53 0.5 BYK-333 0.5 additive Leveling agent 3.0 3.0 3.0 3.0 3.0 3.0 Evaluation results 100%M(MPa) 3.2 3.2 3.2 4.1 3.7 7.0 100% hysteresis loss (%) 0.2 0.2 0.2 43.0 25.0 24.0 Elongation (%) 136 136 136 165 145 80 Slippery △ △ △ ○ ○ ○ Solvent resistance ○ ○ ○ ○ ○ ○ SW scratch resistance 500 times X X X X X X

表2、3中，HDI表示六亞甲基二異氰酸酯，氫化MDI表示氫化二苯基甲烷二異氰酸酯，AK1000表示二甲基聚矽氧油(AK1000、旭化成WACKER聚矽氧股份有限公司製)，AK10000表示二甲基聚矽氧油(AK10000、旭化成WACKER聚矽氧股份有限公司製)，AK100000表示二甲基聚矽氧油(AK100000、旭化成WACKER聚矽氧股份有限公司製)，C800表示聚矽氧乳化液(C800、旭化成WACKER聚矽氧股份有限公司製)，KF53表示甲基苯基聚矽氧油(KF-53、信越矽利光股份有限公司製)，BYK-333表示聚醚改質聚二甲基矽氧烷(BYK-333、BYK･Japan股份有限公司製)。In Tables 2 and 3, HDI means hexamethylene diisocyanate, hydrogenated MDI means hydrogenated diphenylmethane diisocyanate, AK1000 means dimethyl polysiloxane oil (AK1000, manufactured by Asahi Kasei Wacker Polysiloxane Co., Ltd.), AK10000 It means dimethyl polysiloxane oil (AK10000, manufactured by Asahi Kasei Wacker Polysiloxane Co., Ltd.), AK100000 means dimethyl polysiloxane oil (AK100000, manufactured by Asahi Kasei Wacker Polysiloxane Co., Ltd.), and C800 means polysiloxane Emulsion (C800, manufactured by Asahi Kasei WACKER Polysiloxane Co., Ltd.), KF53 means methyl phenyl polysiloxane oil (KF-53, manufactured by Shin-Etsu Silicone Co., Ltd.), BYK-333 means polyether modified polysiloxane Methylsiloxane (BYK-333, manufactured by BYK･Japan Co., Ltd.).

實施例1~9為本發明之實施例，可兼具柔軟性、與耐擦傷性。比較例1~3係未滿足滑性的要件之例子，比較例4、5係未滿足磁滯損失的要件之例子，比較例6係未滿足100%模數及磁滯損失的要件之例子，任一者皆耐擦傷性不足。Examples 1-9 are examples of the present invention, which can have both flexibility and scratch resistance. Comparative Examples 1 to 3 are examples that do not meet the requirements for slippage, Comparative Examples 4 and 5 are examples that do not meet the requirements for hysteresis loss, and Comparative Example 6 is an example that does not meet the requirements for 100% modulus and hysteresis loss. Either one has insufficient scratch resistance.

無。no.

無。no.

無。no.

Claims (5)

一種樹脂成形體，其係利用下述方法所測定之100%模數為5MPa以下， 利用下述方法所測定之100%伸長回復時的磁滯損失為20%以下，且 利用下述方法所測定之動摩擦力為2kN以下； [100%模數之測定方法] 將成形為厚度30μm、寬5mm、長度50mm，且在溫度23℃的環境下，使用拉伸試驗機，以初期的卡盤間距離40mm、拉伸速度10mm/秒之條件進行伸長，並進行了100%伸長時的應力，設為100%模數； [100%伸長回復時的磁滯損失之測定方法] 成形為厚度30μm、寬5mm、長度50mm，且在溫度23℃的環境下，使用拉伸試驗機，以初期的卡盤間距離40mm、伸長速度10mm/秒之條件進行伸長，進行了100%伸長後，立即以卡盤間距離40mm、伸縮速度10mm/秒之條件使其伸縮；此時，將從所施加的負載與變形量之圖表的積分值，自試驗片在拉伸時被施予的熱量與在拉回時試驗片所放出的熱量之差所求出之熱量的損失比例，設為磁滯損失； [摩擦力之測定方法] 將成形為厚度30μm、寬5mm、長度50mm，且在溫度23℃的環境下，使負載為200gf，並使用直徑10mm的不鏽鋼製球壓頭，而以試驗速度120cm/分鐘之條件所測定之摩擦力，設為動摩擦力。A resin molded body whose 100% modulus measured by the following method is 5 MPa or less, The hysteresis loss at 100% elongation recovery measured by the following method is less than 20%, and The dynamic friction force measured by the following method is less than 2kN; [Method of measuring 100% modulus] It was formed into a thickness of 30μm, a width of 5mm, and a length of 50mm, and in an environment with a temperature of 23°C, using a tensile testing machine, the initial distance between the chucks was 40mm and the tensile speed was 10mm/sec. The stress at 100% elongation is set to 100% modulus; [Measuring method of hysteresis loss at 100% elongation recovery] It was formed into a thickness of 30μm, a width of 5mm, and a length of 50mm, and under the environment of a temperature of 23℃, using a tensile testing machine, the initial distance between the chucks was 40mm and the elongation speed was 10mm/sec. After that, immediately expand and contract under the conditions of a distance between the chucks of 40mm and an expansion speed of 10mm/sec. At this time, the integral value of the graph of the applied load and the amount of deformation will be applied from the test piece when it is stretched. The heat loss ratio calculated by the difference between the heat and the heat released by the test piece when it is pulled back is set as the hysteresis loss; [Measurement method of friction force] It is formed into a thickness of 30μm, a width of 5mm, and a length of 50mm. The friction is measured under the conditions of a test speed of 120cm/min with a load of 200gf at a temperature of 23°C and a stainless steel ball indenter with a diameter of 10mm. Force, set as dynamic friction force. 如請求項1之樹脂成形體，其包含聚胺基甲酸酯樹脂。The resin molded body according to claim 1, which contains a polyurethane resin. 如請求項1或2之樹脂成形體，其中下述式(1)所示之化合物的含有率為0.1質量%以上3質量%以下，
Figure 03_image003
[式(1)中，R1 、R2 各自獨立地表示甲基或羥基；n表示1~3,000之整數]。The resin molded body of claim 1 or 2, wherein the content of the compound represented by the following formula (1) is 0.1% by mass to 3% by mass,
Figure 03_image003
[In formula (1), R 1 and R 2 each independently represent a methyl group or a hydroxyl group; n represents an integer of 1 to 3,000]. 一種積層體 ，其具有基材、與如請求項1至3中任一項之樹脂成形體。A laminated body having a base material and a resin molded body according to any one of claims 1 to 3. 一種物品，其具有如請求項1至3中任一項之樹脂成形體或如請求項4之積層體。An article having a resin molded body as claimed in any one of claims 1 to 3 or a laminated body as claimed in claim 4.
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