TWI839801B - Polyisocyanate composition, cured film, adhesive resin composition, adhesive resin sheet, and laminated film - Google Patents

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

Info

Publication number
TWI839801B
TWI839801B TW111129090A TW111129090A TWI839801B TW I839801 B TWI839801 B TW I839801B TW 111129090 A TW111129090 A TW 111129090A TW 111129090 A TW111129090 A TW 111129090A TW I839801 B TWI839801 B TW I839801B
Authority
TW
Taiwan
Prior art keywords
mass
polyisocyanate composition
adhesive resin
group
parts
Prior art date
Application number
TW111129090A
Other languages
Chinese (zh)
Other versions
TW202313748A (en
Inventor
東昌嗣
武井麗
Original Assignee
日商旭化成股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商旭化成股份有限公司 filed Critical 日商旭化成股份有限公司
Publication of TW202313748A publication Critical patent/TW202313748A/en
Application granted granted Critical
Publication of TWI839801B publication Critical patent/TWI839801B/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269Lactones
    • C08G18/4277Caprolactone and/or substituted caprolactone
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/73Polyisocyanates or polyisothiocyanates acyclic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • C08L75/06Polyurethanes from polyesters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/06Polyurethanes from polyesters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • C09J175/06Polyurethanes from polyesters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35Heat-activated
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/40Adhesives in the form of films or foils characterised by release liners

Landscapes

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

Abstract

本發明提供一種聚異氰酸酯組合物等,該聚異氰酸酯組合物係由選自由脂肪族二異氰酸酯及脂環族二異氰酸酯所組成之群中之至少1種二異氰酸酯、及選自由數量平均分子量Mn為500以上之二官能聚酯多元醇(A)及數量平均分子量Mn為500以上之三官能以上之聚酯多元醇(B)所組成之群中之至少1種聚酯多元醇衍生,上述二異氰酸酯之異氰酸基相對於上述聚酯多元醇之羥基之莫耳比為1.5以上30.0以下,上述聚異氰酸酯組合物之重量平均分子量為1400以上800000以下。The present invention provides a polyisocyanate composition, etc. The polyisocyanate composition is derived from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and at least one polyester polyol selected from the group consisting of a difunctional polyester polyol (A) having a number average molecular weight Mn of 500 or more and a trifunctional or higher polyester polyol (B) having a number average molecular weight Mn of 500 or more, wherein the molar ratio of the isocyanate group of the diisocyanate to the hydroxyl group of the polyester polyol is 1.5 to 30.0, and the weight average molecular weight of the polyisocyanate composition is 1400 to 800000.

Description

聚異氰酸酯組合物、硬化膜、黏著性樹脂組合物、黏著性樹脂片材、及積層膜Polyisocyanate composition, cured film, adhesive resin composition, adhesive resin sheet, and laminated film

本發明係關於一種聚異氰酸酯組合物、硬化膜、黏著性樹脂組合物、黏著性樹脂片材、及積層膜。 The present invention relates to a polyisocyanate composition, a hardened film, an adhesive resin composition, an adhesive resin sheet, and a laminate film.

近年來,塑膠膜或黏接著劑由於具有廣泛之功能,故而於各種領域中使用。於此種情況下,不僅向平坦部位之應用增加,向曲面部或具有彎折運動之部位之類的此前較少之用途之應用亦增加。例如,可例舉比如軟性顯示器或可摺疊顯示器、汽車之構件等之貼合,近年來需求迅速擴大。隨之,針對曲面或彎曲,要求追隨性、伸縮性及耐彎曲性良好且強韌之高柔軟性膜或黏接著劑。又,對於光學用途,同時亦要求較高之透明性,具體為霧度值為3.0%以下。 In recent years, plastic films or adhesives have been used in various fields due to their wide range of functions. In this case, applications have increased not only to flat parts, but also to curved parts or parts with bending movements, which were previously less common. For example, the bonding of flexible displays or foldable displays, automotive components, etc. has seen a rapid increase in demand in recent years. As a result, for curved surfaces or bends, highly flexible films or adhesives with good tracking, stretchability, and bending resistance and strong toughness are required. In addition, for optical uses, higher transparency is also required, specifically a haze value of 3.0% or less.

例如,專利文獻1中揭示一種具有伸展性之聚胺基甲酸酯塗料用預聚物之製造方法,該方法包括使脂肪族二異氰酸酯或脂環族二異氰酸酯與數量平均分子量為500以上1500以下之聚己內酯二醇及/或三醇發生反應。又,專利文獻2中揭示一種混合物,該混合物係使脂肪族二異氰酸酯或脂環族二異氰酸酯與數量平均分子量為700以上1500以下之聚四亞甲基二醇 發生反應所得之預聚物、與使脂肪族二異氰酸酯或脂環族二異氰酸酯與數量平均分子量為500以上1500以下之聚己內酯多元醇發生反應所得之預聚物的混合物。 For example, Patent Document 1 discloses a method for producing a prepolymer for polyurethane coating having stretchability, which method comprises reacting an aliphatic diisocyanate or alicyclic diisocyanate with a polycaprolactone diol and/or triol having a number average molecular weight of 500 to 1500. In addition, Patent Document 2 discloses a mixture, which is a mixture of a prepolymer obtained by reacting an aliphatic diisocyanate or alicyclic diisocyanate with a polytetramethylene glycol having a number average molecular weight of 700 to 1500, and a prepolymer obtained by reacting an aliphatic diisocyanate or alicyclic diisocyanate with a polycaprolactone polyol having a number average molecular weight of 500 to 1500.

[先前技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開昭61-028518號公報 [Patent document 1] Japanese Patent Publication No. 61-028518

[專利文獻2]日本專利特開平02-001718號公報 [Patent document 2] Japanese Patent Publication No. 02-001718

然而,專利文獻1或專利文獻2等中記載之先前之藉由聚酯多元醇或聚醚多元醇改性之聚異氰酸酯之柔軟性有改良之餘地。又,於該等文獻中,研究僅限於塗料用途,未對於黏接著劑中之應用進行具體研究,進而,完全未著眼於聚異氰酸酯之結構與透明性之相關性。 However, the softness of the polyisocyanate modified by polyester polyol or polyether polyol described in Patent Document 1 or Patent Document 2 etc. has room for improvement. Moreover, in these documents, the research is limited to the use in coatings, and no specific research is conducted on the application in adhesives. Furthermore, no attention is paid to the correlation between the structure and transparency of polyisocyanate.

本發明係鑒於上述情況而成,提供一種聚異氰酸酯組合物,其能夠獲得使聚異氰酸酯組合物單獨硬化而成之硬化膜之柔軟性及透明性良好且伸長率及拉伸斷裂應力優異之硬化膜、以及黏著力、硬化性及透明性優異之黏著性樹脂組合物及黏著性樹脂片材。又,本發明提供一種具備上述黏著性樹脂片材之積層膜。 The present invention is made in view of the above situation, and provides a polyisocyanate composition, which can obtain a cured film formed by curing the polyisocyanate composition alone, which has good flexibility and transparency, and excellent elongation and tensile fracture stress, as well as an adhesive resin composition and an adhesive resin sheet with excellent adhesion, curability and transparency. In addition, the present invention provides a laminated film having the above-mentioned adhesive resin sheet.

即,本發明包含以下形態。 That is, the present invention includes the following forms.

(1)一種聚異氰酸酯組合物,其係由選自由脂肪族二異氰酸酯及脂環族二異氰酸酯所組成之群中之至少1種二異氰酸酯、及選自由數量平均分子量Mn為500以上之二官能聚酯多元醇(A)及數量平均分子量Mn為500以上之三官能以上之聚酯多元醇(B)所組成之群中之至少1種聚酯多元醇衍生,上述二異氰酸酯之異氰酸基相對於上述聚酯多元醇之羥基之莫耳比為1.5以上30.0以下,上述聚異氰酸酯組合物之重量平均分子量為1400以上800000以下。 (1) A polyisocyanate composition, which is derived from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and at least one polyester polyol selected from the group consisting of a difunctional polyester polyol (A) having a number average molecular weight Mn of 500 or more and a trifunctional or higher polyester polyol (B) having a number average molecular weight Mn of 500 or more, wherein the molar ratio of the isocyanate group of the diisocyanate to the hydroxyl group of the polyester polyol is 1.5 or more and 30.0 or less, and the weight average molecular weight of the polyisocyanate composition is 1400 or more and 800000 or less.

(2)如(1)所記載之聚異氰酸酯組合物,其中上述聚異氰酸酯組合物之平均異氰酸基官能基數為2.0以上6.0以下。 (2) The polyisocyanate composition as described in (1), wherein the average number of isocyanate functional groups of the polyisocyanate composition is greater than 2.0 and less than 6.0.

(3)如(1)或(2)所記載之聚異氰酸酯組合物,其中上述聚異氰酸酯組合物之異氰酸基含有率為1.0質量%以上8.7質量%以下。 (3) The polyisocyanate composition as described in (1) or (2), wherein the isocyanate group content of the polyisocyanate composition is not less than 1.0 mass % and not more than 8.7 mass %.

(4)如(1)至(3)中任一項所記載之聚異氰酸酯組合物,其中相對於上述二異氰酸酯100質量份,上述聚酯多元醇(A)之含量為0.1質量份以上900質量份以下,相對於上述二異氰酸酯100質量份,上述聚酯多元醇(B)之含量為0.1質量份以上900質量份以下。 (4) A polyisocyanate composition as described in any one of (1) to (3), wherein the content of the polyester polyol (A) is 0.1 to 900 parts by mass relative to 100 parts by mass of the diisocyanate, and the content of the polyester polyol (B) is 0.1 to 900 parts by mass relative to 100 parts by mass of the diisocyanate.

(5)如(1)至(4)中任一項所記載之聚異氰酸酯組合物,其中上述聚酯多元醇係聚己內酯多元醇。 (5) A polyisocyanate composition as described in any one of (1) to (4), wherein the polyester polyol is a polycaprolactone polyol.

(6)如(1)至(5)中任一項所記載之聚異氰酸酯組合物,其塗敷於玻璃上並於23℃、65%濕度環境下保管168小時後形成之膜厚為40μm之硬化膜於23℃環境下之柯尼希(König)硬度為60次以下。 (6) The polyisocyanate composition described in any one of (1) to (5), when applied on glass and stored at 23°C and 65% humidity for 168 hours, forms a cured film with a thickness of 40 μm and a König hardness of 60 times or less at 23°C.

(7)如(6)所記載之聚異氰酸酯組合物,其中於將膜厚為40μm之上述硬化膜貼附於霧度值為0.1%之玻璃上之狀態下藉由霧度計測定之霧度值為3.0%以下。 (7) The polyisocyanate composition described in (6), wherein the haze value measured by a haze meter when the cured film having a film thickness of 40 μm is attached to a glass having a haze value of 0.1% is 3.0% or less.

(8)一種硬化膜,其係包含如(1)至(5)中任一項所記載之聚異氰酸酯組合物、及玻璃轉移溫度為0℃以上100℃以下之多元醇的樹脂組合物之硬化膜,以速度20mm/分鐘測定之拉伸試驗中之伸長率為140%以上,伸長率為140%時之應力為25.0MPa以下,且拉伸斷裂應力為上述伸長率為140%時之應力之1.2倍以上。 (8) A cured film comprising a polyisocyanate composition as described in any one of (1) to (5) and a resin composition of a polyol having a glass transition temperature of 0°C to 100°C, wherein the elongation in a tensile test measured at a speed of 20 mm/min is 140% or more, the stress at 140% is 25.0 MPa or less, and the tensile fracture stress is 1.2 times or more of the stress at 140% above the elongation.

(9)如(8)所記載之硬化膜,其中相對於上述多元醇100質量份,上述聚異氰酸酯組合物之含量為0.01質量份以上200質量份以下。 (9) A cured film as described in (8), wherein the content of the polyisocyanate composition is not less than 0.01 parts by mass and not more than 200 parts by mass relative to 100 parts by mass of the polyol.

(10)一種黏著性樹脂組合物,其包含如(1)至(7)中任一項所記載之聚異氰酸酯組合物、及玻璃轉移溫度為0.0℃以下之含有交聯性官能基之聚合物。 (10) An adhesive resin composition comprising a polyisocyanate composition as described in any one of (1) to (7), and a polymer containing a crosslinking functional group having a glass transition temperature of 0.0°C or less.

(11)如(10)所記載之黏著性樹脂組合物,其中上述含有交聯性官能基之聚合物係丙烯酸系聚合物或胺基甲酸酯系聚合物。 (11) The adhesive resin composition described in (10), wherein the polymer containing the cross-linking functional group is an acrylic polymer or a urethane polymer.

(12)如(10)或(11)所記載之黏著性樹脂組合物,其中上述含有交聯性官能基之聚合物係使具有交聯性官能基之聚合性(甲基)丙烯酸單體、與酯基末端之碳數為1以上18以下之(甲基)丙烯酸酯單體共聚而成,且玻璃轉移溫度Tg為-75.0℃以上0.0℃以下。 (12) The adhesive resin composition as described in (10) or (11), wherein the polymer containing a crosslinking functional group is obtained by copolymerizing a polymerizable (meth) acrylic monomer having a crosslinking functional group and a (meth) acrylic ester monomer having a carbon number of 1 to 18 at the end of the ester group, and the glass transition temperature Tg is between -75.0°C and 0.0°C.

(13)如(10)至(12)中任一項所記載之黏著性樹脂組合物,其中上述含有交聯性官能基之聚合物之重量平均分子量為1.0×105以上5.0×106以下。 (13) The adhesive resin composition as described in any one of (10) to (12), wherein the weight average molecular weight of the polymer containing a crosslinking functional group is 1.0×10 5 or more and 5.0×10 6 or less.

(14)如(10)至(13)中任一項所記載之黏著性樹脂組合物,其中上述交 聯性官能基係選自由羥基、環氧基、氧雜環丁基、羧基、乙烯基、及胺基所組成之群中之1種以上。 (14) The adhesive resin composition as described in any one of (10) to (13), wherein the cross-linking functional group is selected from at least one of the group consisting of hydroxyl, epoxy, cyclobutyl, carboxyl, vinyl, and amino.

(15)如(10)至(14)中任一項所記載之黏著性樹脂組合物,其中相對於上述含有交聯性官能基之聚合物100質量份,上述聚異氰酸酯組合物之含量為0.01質量份以上20.00質量份以下。 (15) An adhesive resin composition as described in any one of (10) to (14), wherein the content of the polyisocyanate composition is not less than 0.01 parts by mass and not more than 20.00 parts by mass relative to 100 parts by mass of the polymer containing crosslinking functional groups.

(16)一種黏著性樹脂片材,其係使如(10)至(15)中任一項所記載之黏著性樹脂組合物藉由熱或光發生硬化而成。 (16) An adhesive resin sheet, which is obtained by hardening the adhesive resin composition described in any one of (10) to (15) by heat or light.

(17)如(16)所記載之黏著性樹脂片材,其中上述黏著性樹脂片材之厚度為1μm以上1000μm以下。 (17) The adhesive resin sheet as described in (16), wherein the thickness of the adhesive resin sheet is greater than 1 μm and less than 1000 μm.

(18)如(16)或(17)所記載之黏著性樹脂片材,其凝膠分率為20.0質量%以上99.9質量%以下。 (18) The adhesive resin sheet described in (16) or (17), wherein the gel fraction is not less than 20.0 mass % and not more than 99.9 mass %.

(19)如(16)至(18)中任一項所記載之黏著性樹脂片材,其於23℃下以300mm/分鐘之速度測定之180度剝離黏著力為0.05N/20mm以上65.00N/20mm以下。 (19) The adhesive resin sheet described in any one of (16) to (18), wherein the 180-degree peeling adhesion measured at 23°C and a speed of 300 mm/min is 0.05 N/20 mm or more and 65.00 N/20 mm or less.

(20)如(16)至(19)中任一項所記載之黏著性樹脂片材,其將厚度50μm之黏著性樹脂片材貼附於霧度值為0.1%之玻璃上並藉由霧度計測定之霧度值為2.0%以下。 (20) An adhesive resin sheet as described in any one of (16) to (19), wherein the adhesive resin sheet having a thickness of 50 μm is attached to a glass having a haze value of 0.1% and the haze value measured by a haze meter is less than 2.0%.

(21)一種積層膜,其係於如(16)至(20)中任一項所記載之黏著性樹脂片材之至少一個面上積層有膜基材者。 (21) A laminated film, which is a film substrate laminated on at least one surface of the adhesive resin sheet described in any one of (16) to (20).

(22)如(21)所記載之積層膜,其中上述膜基材係選自由聚酯系樹脂、乙酸酯系樹脂、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、(甲基)丙烯酸系樹脂、聚氯乙烯系樹脂、聚偏二氯乙烯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、聚芳酯系樹脂、聚 苯硫醚系樹脂、三乙醯纖維素系樹脂所組成之群中之至少1種。 (22) A laminate film as described in (21), wherein the film substrate is at least one selected from the group consisting of polyester resins, acetate resins, polyether sulfide resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, and triacetylcellulose resins.

(23)如(21)或(22)所記載之積層膜,其中上述積層膜用於光學用途。 (23) A multilayer film as described in (21) or (22), wherein the multilayer film is used for optical purposes.

根據上述形態之聚異氰酸酯組合物,能夠提供一種聚異氰酸酯組合物,其能夠獲得使聚異氰酸酯組合物單獨硬化而成之硬化膜之柔軟性及透明性良好且伸長率及拉伸斷裂應力優異之硬化膜、以及黏著力、硬化性及透明性優異之黏著性樹脂組合物及黏著性樹脂片材。又,本發明能夠提供一種具備上述黏著性樹脂片材之積層膜。 According to the polyisocyanate composition of the above-mentioned form, a polyisocyanate composition can be provided, which can obtain a cured film formed by curing the polyisocyanate composition alone, which has good flexibility and transparency, and excellent elongation and tensile fracture stress, as well as an adhesive resin composition and an adhesive resin sheet with excellent adhesion, curability and transparency. In addition, the present invention can provide a laminated film having the above-mentioned adhesive resin sheet.

再者,於本說明書中,「多元醇」意指一分子中具有2個以上羥基(-OH)之化合物。 Furthermore, in this specification, "polyol" means a compound having two or more hydroxyl groups (-OH) in one molecule.

又,於本說明書中,「聚異氰酸酯」意指具有2個以上異氰酸基(-NCO)之複數個單體化合物結合所得之反應產物。 In addition, in this specification, "polyisocyanate" means a reaction product obtained by combining multiple monomer compounds having two or more isocyanate groups (-NCO).

又,於本說明書中,除非特別說明,否則「(甲基)丙烯酸」包含甲基丙烯酸與丙烯酸,「(甲基)丙烯酸酯」包含甲基丙烯酸酯與丙烯酸酯。 In addition, in this specification, unless otherwise specified, "(meth)acrylic acid" includes methacrylic acid and acrylic acid, and "(meth)acrylate" includes methacrylate and acrylate.

《聚異氰酸酯組合物》 《Polyisocyanate composition》

本實施方式之聚異氰酸酯組合物係由二異氰酸酯、及選自由數量平均分子量為500以上之二官能聚酯多元醇(A)(以下僅稱為「聚酯多元醇(A)」)及數量平均分子量Mn為500以上之三官能以上之聚酯多元醇(B)(以下僅稱為「聚酯多元醇(B)」)所組成之群中之至少1種聚酯多元醇衍生。 即,本實施方式之聚異氰酸酯組合物係二異氰酸酯與上述1種以上聚酯多元醇之反應產物,包含藉由1種以上之上述聚酯多元醇改性之聚異氰酸酯。二異氰酸酯係選自由脂肪族二異氰酸酯及脂環族二異氰酸酯所組成之群中之至少1種。 The polyisocyanate composition of the present embodiment is derived from a diisocyanate and at least one polyester polyol selected from the group consisting of a bifunctional polyester polyol (A) having a number average molecular weight of 500 or more (hereinafter referred to as "polyester polyol (A)") and a trifunctional or higher polyester polyol (B) having a number average molecular weight Mn of 500 or more (hereinafter referred to as "polyester polyol (B)"). That is, the polyisocyanate composition of the present embodiment is a reaction product of a diisocyanate and one or more of the above polyester polyols, including a polyisocyanate modified by one or more of the above polyester polyols. The diisocyanate is at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.

於本實施方式之聚異氰酸酯組合物中,二異氰酸酯之異氰酸基相對於聚酯多元醇(A)及/或聚酯多元醇(B)之羥基之莫耳比(異氰酸基/羥基之莫耳比)為1.5以上30.0以下,較佳為2.0以上25.0以下,更佳為2.1以上23.0以下,進而較佳為2.2以上20.0以下,進而較佳為2.3以上20.0以下,進而較佳為2.4以上20.0以下,尤佳為2.5以上20.0以下,最佳為2.52以上20.0以下。 In the polyisocyanate composition of the present embodiment, the molar ratio of the isocyanate group of the diisocyanate to the hydroxyl group of the polyester polyol (A) and/or the polyester polyol (B) (molar ratio of isocyanate group/hydroxyl group) is 1.5 to 30.0, preferably 2.0 to 25.0, more preferably 2.1 to 23.0, further preferably 2.2 to 20.0, further preferably 2.3 to 20.0, further preferably 2.4 to 20.0, particularly preferably 2.5 to 20.0, and most preferably 2.52 to 20.0.

異氰酸基/羥基之莫耳比例如可使用聚異氰酸酯組合物之製造時所使用之聚酯多元醇(A)及/或聚酯多元醇(B)之羥基之莫耳量、及二異氰酸酯之異氰酸基之莫耳量而算出。 The molar ratio of isocyanate group/hydroxyl group can be calculated, for example, using the molar amount of hydroxyl group of polyester polyol (A) and/or polyester polyol (B) used in the preparation of the polyisocyanate composition and the molar amount of isocyanate group of diisocyanate.

本實施方式之聚異氰酸酯組合物之重量平均分子量為1400以上,較佳為1500以上,更佳為2000以上,進而較佳為2500以上,尤佳為3000以上。 The weight average molecular weight of the polyisocyanate composition of this embodiment is 1400 or more, preferably 1500 or more, more preferably 2000 or more, further preferably 2500 or more, and particularly preferably 3000 or more.

本實施方式之聚異氰酸酯組合物之重量平均分子量之上限值並無特別限定,可設為800000。 The upper limit of the weight average molecular weight of the polyisocyanate composition of this embodiment is not particularly limited and can be set to 800,000.

本實施方式之聚異氰酸酯組合物之重量平均分子量例如可藉由凝膠滲透層析法(以下有時簡記為「GPC」)進行測定。 The weight average molecular weight of the polyisocyanate composition of this embodiment can be measured, for example, by gel permeation chromatography (hereinafter sometimes abbreviated as "GPC").

本實施方式之聚異氰酸酯組合物由於具有上述構成,故而使聚異氰酸酯組合物單獨硬化而成之硬化膜之硬度低於先前,柔軟性及透明性良好。又,藉由使用本實施方式之聚異氰酸酯組合物,能夠獲得伸長率為140%時之應力低於先前、伸長率高於先前且拉伸斷裂應力高於先前之硬化膜。進而,藉由使用本實施方式之聚異氰酸酯組合物,能夠獲得黏著力、硬化性及透明性優異之黏著性樹脂片材。 Since the polyisocyanate composition of this embodiment has the above-mentioned structure, the hardness of the cured film formed by curing the polyisocyanate composition alone is lower than before, and the softness and transparency are good. In addition, by using the polyisocyanate composition of this embodiment, a cured film with a stress lower than before at an elongation of 140%, a higher elongation than before, and a higher tensile fracture stress than before can be obtained. Furthermore, by using the polyisocyanate composition of this embodiment, an adhesive resin sheet with excellent adhesion, curability and transparency can be obtained.

其次,以下對本實施方式之聚異氰酸酯組合物之各構成成分詳細進行說明。 Next, the components of the polyisocyanate composition of this embodiment are described in detail below.

<聚異氰酸酯> <Polyisocyanate>

聚異氰酸酯係一分子中具有來自二異氰酸酯及1種以上之上述聚酯多元醇之結構單元者。 Polyisocyanate is a compound that contains structural units derived from diisocyanate and one or more of the above-mentioned polyester polyols in one molecule.

本實施方式之聚異氰酸酯組合物於由二異氰酸酯以及聚酯多元醇(A)及聚酯多元醇(B)衍生之情形時,可為一分子中具有來自二異氰酸酯以及聚酯多元醇(A)及聚酯多元醇(B)之所有結構單元之聚異氰酸酯,亦可為一分子中具有來自二異氰酸酯及聚酯多元醇(A)之結構單元之聚異氰酸酯、與一分子中具有來自二異氰酸酯及聚酯多元醇(B)之結構單元之聚異氰酸酯之混合物。 When the polyisocyanate composition of the present embodiment is derived from diisocyanate and polyester polyol (A) and polyester polyol (B), it may be a polyisocyanate having all structural units derived from diisocyanate and polyester polyol (A) and polyester polyol (B) in one molecule, or a mixture of a polyisocyanate having structural units derived from diisocyanate and polyester polyol (A) in one molecule and a polyisocyanate having structural units derived from diisocyanate and polyester polyol (B) in one molecule.

聚異氰酸酯具有選自由脲基甲酸酯結構、脲二酮結構、亞胺基

Figure 111129090-A0305-02-0009-5
Figure 111129090-A0305-02-0009-6
二酮結構、異氰尿酸酯結構、尿素結構、胺基甲酸酯結構、及縮二脲結 構所組成之群中之至少1種以上之結構。其中,較佳為具有選自由胺基甲酸酯結構、脲基甲酸酯結構、縮二脲結構、尿素結構、脲二酮結構、及異氰尿酸酯結構所組成之群中之至少1種結構,更佳為具有選自由胺基甲酸酯結構、脲基甲酸酯結構、縮二脲結構、尿素結構、及脲二酮結構所組成之群中之至少1種結構,進而較佳為具有選自由胺基甲酸酯結構、脲基甲酸酯結構、尿素結構、及脲二酮結構所組成之群中之至少1種結構,進而較佳為具有選自由胺基甲酸酯結構、脲基甲酸酯結構、及脲二酮結構所組成之群中之至少1種結構,進而較佳為具有選自由胺基甲酸酯結構、脲基甲酸酯結構所組成之群中之至少1種結構,尤佳為具有胺基甲酸酯結構。 The polyisocyanate has an allophanate structure, a uretdione structure, an imine structure,
Figure 111129090-A0305-02-0009-5
two
Figure 111129090-A0305-02-0009-6
The present invention relates to a hydroxyl group-containing ester having at least one structure selected from the group consisting of a diketone structure, an isocyanurate structure, a urea structure, a carbamate structure, and a biuret structure. Among them, it is preferred to have at least one structure selected from the group consisting of a carbamate structure, an allophanate structure, a biuret structure, a urea structure, a uretdione structure, and an isocyanurate structure, and it is more preferred to have at least one structure selected from the group consisting of a carbamate structure, an allophanate structure, a biuret structure, a urea structure, and a uretdione structure, and it is further preferred to have at least one structure selected from the group consisting of a carbamate structure, an allophanate structure, a biuret structure, a urea structure, and a uretdione structure. The present invention further preferably has at least one structure selected from the group consisting of an ester structure, an allophanate structure, a urea structure, and a uretdione structure, and further preferably has at least one structure selected from the group consisting of a carbamate structure, an allophanate structure, and a uretdione structure, and further preferably has at least one structure selected from the group consisting of a carbamate structure and an allophanate structure, and particularly preferably has a carbamate structure.

[二異氰酸酯] [Diisocyanate]

二異氰酸酯係選自由脂肪族二異氰酸酯及脂環族二異氰酸酯所組成之群中之至少1種。 The diisocyanate is at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.

作為脂肪族二異氰酸酯,例如,可例舉1,4-二異氰酸基丁烷、1,5-二異氰酸基戊烷、(2,6-二異氰酸基)己酸乙酯、1,6-二異氰酸基己烷(以下有時簡記為「HDI」)、1,9-二異氰酸基壬烷、1,12-二異氰酸基十二烷、2,2,4-或2,4,4-三甲基-1、6-二異氰酸基己烷等,但並未限定於以上。可單獨使用該等脂肪族二異氰酸酯,亦可將2種以上該等脂肪族二異氰酸酯組合使用。 Examples of aliphatic diisocyanates include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, (2,6-diisocyanato)hexanoic acid ethyl ester, 1,6-diisocyanatohexane (hereinafter sometimes referred to as "HDI"), 1,9-diisocyanatononane, 1,12-diisocyanatododecane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, etc., but are not limited thereto. These aliphatic diisocyanates may be used alone or in combination of two or more.

作為脂環族二異氰酸酯,例如,可例舉1,3-或1,4-雙(異氰酸基甲基)環己烷(以下、有時簡記為「氫化XDI」)、1,3-或1,4-二異氰酸基環己烷、 3,5,5-三甲基1-異氰酸基-3-(異氰酸基甲基)環己烷(以下有時簡記為「IPDI」)、4-4'-二異氰酸基-二環己基甲烷(以下有時簡記為「氫化MDI」)、2,5-或2,6-二異氰酸基甲基降

Figure 111129090-A0305-02-0011-7
烷等,但並未限定於以上。可單獨使用1種該等脂環族二異氰酸酯,亦可將2種以上該等脂環族二異氰酸酯組合使用。 Examples of the alicyclic diisocyanate include 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (hereinafter, sometimes referred to as "hydrogenated XDI"), 1,3- or 1,4-diisocyanatocyclohexane, 3,5,5-trimethyl-1-isocyanato-3-(isocyanatomethyl)cyclohexane (hereinafter, sometimes referred to as "IPDI"), 4-4'-diisocyanato-dicyclohexylmethane (hereinafter, sometimes referred to as "hydrogenated MDI"), 2,5- or 2,6-diisocyanatomethylcyclohexane.
Figure 111129090-A0305-02-0011-7
Such alicyclic diisocyanates may be used alone or in combination of two or more.

可單獨使用該等脂肪族二異氰酸酯及脂環族二異氰酸酯之任一,亦可將2種以上脂肪族二異氰酸酯及脂環族二異氰酸酯組合使用。 Any of the aliphatic diisocyanates and alicyclic diisocyanates may be used alone, or two or more aliphatic diisocyanates and alicyclic diisocyanates may be used in combination.

又,基於柔軟性觀點而言,脂環族二異氰酸酯相對於脂肪族二異氰酸酯之質量比較佳為0/100以上30/70以下。 In addition, from the perspective of softness, the mass ratio of alicyclic diisocyanate to aliphatic diisocyanate is preferably 0/100 or more and 30/70 or less.

其中,作為二異氰酸酯,較佳為1,4-二異氰酸基丁烷、HDI、1,5-五亞甲基二異氰酸酯(PDI)、1,7-二異氰酸基庚烷、1,8-二異氰酸基辛烷、IPDI、氫化XDI、或氫化MDI,更佳為HDI、PDI或IPDI,進而較佳為HDI或PDI,尤佳為HDI。 Among them, as the diisocyanate, 1,4-diisocyanatobutane, HDI, 1,5-pentamethylene diisocyanate (PDI), 1,7-diisocyanatoheptane, 1,8-diisocyanatooctane, IPDI, hydrogenated XDI, or hydrogenated MDI is preferred, HDI, PDI, or IPDI is more preferred, HDI or PDI is further preferred, and HDI is particularly preferred.

聚異氰酸酯之製造除上述二異氰酸酯以外,可進而使用以下所示之異氰酸酯單體。 In the production of polyisocyanates, in addition to the above-mentioned diisocyanates, the following isocyanate monomers can be used.

(1)二苯基甲烷-4,4'-二異氰酸酯(MDI)、1,5-萘二異氰酸酯、甲苯二異氰酸酯(TDI)、苯二甲基二異氰酸酯(XDI)、間四甲基苯二甲基二異氰酸酯(TMXDI)等芳香族二異氰酸酯。 (1) Aromatic diisocyanates such as diphenylmethane-4,4'-diisocyanate (MDI), 1,5-naphthalene diisocyanate, toluene diisocyanate (TDI), xylylene diisocyanate (XDI), and m-tetramethylxylene diisocyanate (TMXDI).

(2)4-異氰酸基甲基-1,8-八亞甲基二異氰酸酯(以下有時稱為「NTI」)、1,3,6-六亞甲基三異氰酸酯(以下有時稱為「HTI」)、雙(2-異 氰酸基乙基)2-異氰酸基戊二酸酯(以下有時稱為「GTI」)、離胺酸三異氰酸酯(以下有時稱為「LTI」)等三異氰酸酯。 (2) Triisocyanates such as 4-isocyanatomethyl-1,8-octamethylene diisocyanate (hereinafter sometimes referred to as "NTI"), 1,3,6-hexamethylene triisocyanate (hereinafter sometimes referred to as "HTI"), bis(2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter sometimes referred to as "GTI"), and lysine triisocyanate (hereinafter sometimes referred to as "LTI").

[聚酯多元醇(A)及聚酯多元醇(B)] [Polyester polyol (A) and polyester polyol (B)]

聚酯多元醇(A)係數量平均分子量為500以上之二官能聚酯多元醇(二醇)。 Polyester polyol (A) is a bifunctional polyester polyol (diol) with a molecular weight of 500 or more.

聚酯多元醇(B)係數量平均分子量為500以上之三官能以上之聚酯多元醇。 Polyester polyol (B) is a trifunctional or higher polyester polyol with a number average molecular weight of 500 or more.

聚酯多元醇(A)之數量平均分子量為500以上,較佳為800以上,更佳為1500以上,進而較佳為1800以上。藉由使聚酯多元醇(A)之數量平均分子量為上述下限值以上,使聚異氰酸酯組合物單獨硬化而成之硬化膜之硬度較低,柔軟性良好。 The number average molecular weight of the polyester polyol (A) is 500 or more, preferably 800 or more, more preferably 1500 or more, and further preferably 1800 or more. By making the number average molecular weight of the polyester polyol (A) above the above lower limit, the hardness of the cured film formed by curing the polyisocyanate composition alone is lower and the softness is good.

另一方面,聚酯多元醇(A)之數量平均分子量之上限值並無特別限定,例如,可設為12000,可設為10000,可設為8000,可設為7000,較佳為設為6000,更佳為設為5000,進而較佳為設為4500。 On the other hand, the upper limit of the number average molecular weight of the polyester polyol (A) is not particularly limited, and can be, for example, 12,000, 10,000, 8,000, 7,000, preferably 6,000, more preferably 5,000, and even more preferably 4,500.

聚酯多元醇(A)之數量平均分子量Mn例如為利用GPC測定所得之基於聚苯乙烯之數量平均分子量。又,於將2種以上聚酯多元醇(A)混合來使用之情形時,算出其等之混合物之數量平均分子量來使用。 The number average molecular weight Mn of the polyester polyol (A) is, for example, the number average molecular weight based on polystyrene obtained by GPC measurement. In addition, when two or more polyester polyols (A) are mixed for use, the number average molecular weight of the mixture is calculated and used.

聚酯多元醇(B)之數量平均分子量為500以上,較佳為800以上。藉由使聚酯多元醇(B)之數量平均分子量為上述下限值以上,使聚異氰酸酯組合物單獨硬化而成之硬化膜之硬度較低,柔軟性良好。 The number average molecular weight of the polyester polyol (B) is 500 or more, preferably 800 or more. By making the number average molecular weight of the polyester polyol (B) above the above lower limit, the hardness of the cured film formed by curing the polyisocyanate composition alone is lower and the softness is good.

另一方面,聚酯多元醇(B)之數量平均分子量之上限值並無特別限定,例如,可設為12000,可設為10000,可設為8000,可設為6000,可設為4000,較佳為設為3500,更佳為設為3000,進而較佳為設為2500。 On the other hand, the upper limit of the number average molecular weight of the polyester polyol (B) is not particularly limited, and can be, for example, 12,000, 10,000, 8,000, 6,000, 4,000, preferably 3,500, more preferably 3,000, and even more preferably 2,500.

聚酯多元醇(B)之數量平均分子量Mn例如為利用GPC測定所得之基於聚苯乙烯之數量平均分子量。又,於將2種以上聚酯多元醇(B)混合來使用之情形時,算出其等之混合物之數量平均分子量來使用。 The number average molecular weight Mn of the polyester polyol (B) is, for example, the number average molecular weight based on polystyrene obtained by GPC measurement. In addition, when two or more polyester polyols (B) are mixed for use, the number average molecular weight of the mixture is calculated and used.

作為聚酯多元醇(A),例如可例舉以下(1)或(2)中之任一種聚酯多元醇等。 As polyester polyol (A), for example, any one of the following polyester polyols (1) or (2) can be cited.

(1)藉由單獨之二元酸或2種以上二元酸之混合物、與單獨之二元醇或2種以上二元醇之混合物之縮合反應所得之聚酯多元醇。 (1) Polyester polyols obtained by the condensation reaction of a single dibasic acid or a mixture of two or more dibasic acids with a single diol or a mixture of two or more diols.

(2)使ε-己內酯藉由二元醇進行開環聚合所得之聚己內酯多元醇。 (2) Polycaprolactone polyol obtained by ring-opening polymerization of ε-caprolactone with diols.

作為上述二元酸,例如,可例舉琥珀酸、己二酸、二聚酸、馬來酸酐、鄰苯二甲酸酐、間苯二甲酸、對苯二甲酸、1,4-環己烷二羧酸等羧酸等。 Examples of the above-mentioned dibasic acid include succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid and other carboxylic acids.

作為上述二元醇,例如,可例舉乙二醇、丙二醇、二乙二醇、1,4-丁二醇、新戊二醇、1,6-己二醇、三甲基戊二醇、環己二醇等。 Examples of the above-mentioned diols include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, etc.

其中,作為聚酯多元醇(A),較佳為二官能聚己內酯多元醇。 Among them, as polyester polyol (A), difunctional polycaprolactone polyol is preferred.

作為市售之二官能聚己內酯多元醇,例如,可例舉Daicel公司製造之商品名「PLACCEL 210」(數量平均分子量1000,羥值112.8mgKOH/g,酸值0.09mgKOH/g)、「PLACCEL 210CP」(數量平均分子量1000,羥值 112.8mgKOH/g,酸值0.16mgKOH/g)、商品名「PLACCEL 212」(數量平均分子量1250,羥值90.8mgKOH/g,酸值0.09mgKOH/g)、商品名「PLACCEL 212CP」(數量平均分子量1250,羥值90.2mgKOH/g,酸值0.14mgKOH/g)、「PLACCEL 220」(數量平均分子量2000,羥值56.7mgKOH/g,酸值0.06mgKOH/g)、「PLACCEL 220CPB」(數量平均分子量2000,羥值57.2mgKOH/g,酸值0.16mgKOH/g)、「PLACCEL 220CPT」(數量平均分子量2000,羥值56.6mgKOH/g,酸值0.02mgKOH/g)、「PLACCEL 230」(數量平均分子量3000,羥值37.6mgKOH/g,酸值0.07mgKOH/g)、「PLACCEL 240(數量平均分子量4000,羥值28.5mgKOH/g,酸值0.07mgKOH/g)等。 Examples of commercially available bifunctional polycaprolactone polyols include "PLACCEL 210" (number average molecular weight 1000, hydroxyl value 112.8 mgKOH/g, acid value 0.09 mgKOH/g), "PLACCEL 210CP" (number average molecular weight 1000, hydroxyl value 112.8 mgKOH/g, acid value 0.16 mgKOH/g), "PLACCEL 212" (number average molecular weight 1250, hydroxyl value 90.8 mgKOH/g, acid value 0.09 mgKOH/g), "PLACCEL 212CP" (number average molecular weight 1250, hydroxyl value 90.2 mgKOH/g, acid value 0.14 mgKOH/g), "PLACCEL "PLACCEL 220" (number average molecular weight 2000, hydroxyl value 56.7mgKOH/g, acid value 0.06mgKOH/g), "PLACCEL 220CPB" (number average molecular weight 2000, hydroxyl value 57.2mgKOH/g, acid value 0.16mgKOH/g), "PLACCEL 220CPT" (number average molecular weight 2000, hydroxyl value 56.6mgKOH/g, acid value 0.02mgKOH/g), "PLACCEL 230" (number average molecular weight 3000, hydroxyl value 37.6mgKOH/g, acid value 0.07mgKOH/g), "PLACCEL 240 (number average molecular weight 4000, hydroxyl value 28.5mgKOH/g, acid value 0.07mgKOH/g), etc.

作為二官能聚己內酯多元醇,基於耐水解性及聚異氰酸酯合成時之反應穩定性之觀點而言,較佳為使用酸值更低者。 As a difunctional polycaprolactone polyol, from the perspective of hydrolysis resistance and reaction stability during polyisocyanate synthesis, it is better to use one with a lower acid value.

作為聚酯多元醇(B),為三官能以上之聚酯多元醇即可,較佳為三官能以上10官能以下之聚酯多元醇,更佳為三官能以上7官能以下之聚酯多元醇,進而較佳為三官能以上5官能以下之聚酯多元醇,尤佳為三官能以上4官能以下之聚酯多元醇,最佳為三官能聚酯多元醇(三醇)。 As the polyester polyol (B), a polyester polyol having three or more functional groups may be used, preferably a polyester polyol having three or more functional groups but less than ten functional groups, more preferably a polyester polyol having three or more functional groups but less than seven functional groups, further preferably a polyester polyol having three or more functional groups but less than five functional groups, particularly preferably a polyester polyol having three or more functional groups but less than four functional groups, and most preferably a trifunctional polyester polyol (triol).

作為三官能聚酯多元醇(B),例如可例舉以下(1)或(2)中之任一種聚酯多元醇等。 As the trifunctional polyester polyol (B), for example, any one of the following polyester polyols (1) or (2) can be cited.

(1)藉由單獨之二元酸或2種以上二元酸之混合物、與單獨之三元醇或2種以上三元醇之混合物之縮合反應所得之聚酯多元醇。 (1) Polyester polyols obtained by the condensation reaction of a single dibasic acid or a mixture of two or more dibasic acids with a single triol or a mixture of two or more triols.

(2)使ε-己內酯藉由三元醇進行開環聚合所得之聚己內酯多元醇。 (2) Polycaprolactone polyol obtained by ring-opening polymerization of ε-caprolactone with triols.

作為上述二元酸,例如,可例舉琥珀酸、己二酸、二聚酸、馬來酸酐、鄰苯二甲酸酐、間苯二甲酸、對苯二甲酸、1,4-環己烷二羧酸等羧酸等。 Examples of the above-mentioned dibasic acid include succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid and other carboxylic acids.

作為上述三元醇,例如,可例舉三羥甲基丙烷、甘油、季戊四醇、2-羥甲基丙二醇、乙氧化三羥甲基丙烷等。 Examples of the above-mentioned triols include trihydroxymethylpropane, glycerin, pentaerythritol, 2-hydroxymethylpropanediol, and ethoxylated trihydroxymethylpropane.

其中,作為三官能聚酯多元醇(B),較佳為三官能聚己內酯多元醇。 Among them, as the trifunctional polyester polyol (B), trifunctional polycaprolactone polyol is preferred.

作為市售之三官能聚己內酯多元醇,例如,可例舉Daicel公司製造之商品名「PLACCEL 305」(數量平均分子量550,羥值305.6mgKOH/g,酸值0.50mgKOH/g)、「PLACCEL 308」(數量平均分子量850,羥值195.3mgKOH/g,酸值0.38mgKOH/g)、「PLACCEL 309」(數量平均分子量900,羥值187.3mgKOH/g,酸值0.20mgKOH/g)、「PLACCEL 312」(數量平均分子量1250,羥值136.1mgKOH/g,酸值0.38mgKOH/g)、「PLACCEL 320」(數量平均分子量2000,羥值85.4mgKOH/g,酸值0.29mgKOH/g)等。 Examples of commercially available trifunctional polycaprolactone polyols include "PLACCEL 305" (number average molecular weight 550, hydroxyl value 305.6 mgKOH/g, acid value 0.50 mgKOH/g), "PLACCEL 308" (number average molecular weight 850, hydroxyl value 195.3 mgKOH/g, acid value 0.38 mgKOH/g), "PLACCEL 309" (number average molecular weight 900, hydroxyl value 187.3 mgKOH/g, acid value 0.20 mgKOH/g), "PLACCEL 312" (number average molecular weight 1250, hydroxyl value 136.1 mgKOH/g, acid value 0.38 mgKOH/g), "PLACCEL 313" (number average molecular weight 1500, hydroxyl value 140.6 mgKOH/g, acid value 0.38 mgKOH/g), "PLACCEL 314" (number average molecular weight 1500, hydroxyl value 140.6 mgKOH/g, acid value 0.38 mgKOH/g), "PLACCEL 315" (number average molecular weight 1500, hydroxyl value 140.6 mgKOH/g, acid value 0.38 mgKOH/g), "PLACCEL 316" (number average molecular weight 1500, hydroxyl value 140.6 mgKOH/g, acid value 0.38 mgKOH/g), "PLACCEL 317" (number average molecular weight 1500, hydroxyl value 140.6 mgKOH/g, acid value 0.38 mgKOH/g), "PLACCEL 318" (number average molecular weight 1500, hydroxyl value 140.6 mgKOH/g, acid value 0.38 mgKOH/g), "PLACCEL 319 320" (number average molecular weight 2000, hydroxyl value 85.4mgKOH/g, acid value 0.29mgKOH/g), etc.

於本實施方式之聚異氰酸酯組合物中,相對於二異氰酸酯100質量份,聚酯多元醇(A)之含量(添加量)較佳為0.1質量份以上900質量份以下,更佳為0.5質量份以上800質量份以下,進而較佳為1質量份以上700質量份以下,進而更佳為1質量份以上600質量份以下。 In the polyisocyanate composition of the present embodiment, the content (addition amount) of the polyester polyol (A) is preferably 0.1 to 900 parts by mass, more preferably 0.5 to 800 parts by mass, more preferably 1 to 700 parts by mass, and more preferably 1 to 600 parts by mass, relative to 100 parts by mass of diisocyanate.

藉由使聚酯多元醇(A)之含量為上述下限值以上,使聚異氰酸酯組合物單獨硬化而成之硬化膜之硬度較低,柔軟性更好。又,能夠獲得黏著力 及硬化性更優異之黏著性樹脂片材。另一方面,藉由使聚酯多元醇(A)之含量為上述上限值以下,於聚異氰酸酯組合物之製造時可不發生凝膠化而維持液體狀態,伸長率及斷裂強度較高,且製成黏著性樹脂片材時之柔軟性更好。 By making the content of polyester polyol (A) above the above lower limit, the hardness of the cured film formed by curing the polyisocyanate composition alone is lower and the flexibility is better. In addition, an adhesive resin sheet with better adhesion and curability can be obtained. On the other hand, by making the content of polyester polyol (A) below the above upper limit, the polyisocyanate composition can be made without gelling and maintained in a liquid state, the elongation and breaking strength are higher, and the flexibility of the adhesive resin sheet is better.

聚酯多元醇(A)之含量例如可由聚異氰酸酯組合物之製造時之二異氰酸酯及聚酯多元醇(A)之調配量、以及所得之聚異氰酸酯組合物之產率而算出。 The content of polyester polyol (A) can be calculated, for example, from the amounts of diisocyanate and polyester polyol (A) formulated during the production of the polyisocyanate composition, and the yield of the obtained polyisocyanate composition.

於本實施方式之聚異氰酸酯組合物中,相對於二異氰酸酯100質量份,聚酯多元醇(B)之含量(添加量)較佳為0.1質量份以上900質量份以下,更佳為0.5質量份以上800質量份以下,進而較佳為1質量份以上700質量份以下,進而更佳為1質量份以上600質量份以下。 In the polyisocyanate composition of the present embodiment, the content (addition amount) of the polyester polyol (B) is preferably 0.1 to 900 parts by mass, more preferably 0.5 to 800 parts by mass, more preferably 1 to 700 parts by mass, and more preferably 1 to 600 parts by mass, relative to 100 parts by mass of diisocyanate.

藉由使聚酯多元醇(B)之含量為上述下限值以上,使聚異氰酸酯組合物單獨硬化而成之硬化膜之硬度較低,柔軟性更好。又,能夠獲得黏著力及硬化性更優異之黏著性樹脂片材。另一方面,藉由使聚酯多元醇(B)之含量為上述上限值以下,於聚異氰酸酯組合物之製造時可不發生凝膠化而維持液體狀態,且製成黏著性樹脂片材時之柔軟性更好。 By making the content of polyester polyol (B) above the above lower limit, the hardness of the cured film formed by curing the polyisocyanate composition alone is lower and the flexibility is better. In addition, an adhesive resin sheet with better adhesion and curability can be obtained. On the other hand, by making the content of polyester polyol (B) below the above upper limit, the polyisocyanate composition can be made without gelling and maintained in a liquid state, and the adhesive resin sheet can be made with better flexibility.

聚酯多元醇(B)之含量例如可由聚異氰酸酯組合物之製造時之二異氰酸酯及聚酯多元醇(B)之調配量、以及所得之聚異氰酸酯組合物之產率而算出。 The content of polyester polyol (B) can be calculated, for example, from the amounts of diisocyanate and polyester polyol (B) formulated during the production of the polyisocyanate composition, and the yield of the obtained polyisocyanate composition.

<聚異氰酸酯組合物之製造方法> <Method for producing polyisocyanate composition>

聚異氰酸酯係使上述二異氰酸酯、與選自由聚酯多元醇(A)及聚酯多 元醇(B)所組成之群中之1種以上聚酯多元醇發生反應而得。以下有時將聚酯多元醇(A)及聚酯多元醇(B)合併僅稱為聚酯多元醇。 The polyisocyanate is obtained by reacting the above-mentioned diisocyanate with one or more polyester polyols selected from the group consisting of polyester polyols (A) and polyester polyols (B). In the following, polyester polyols (A) and polyester polyols (B) may be collectively referred to as polyester polyols.

於將聚酯多元醇(A)及聚酯多元醇(B)組合使用之情形時,聚酯多元醇(A)及聚酯多元醇(B)可分別單獨使用,或以混合物之形態使用。於以混合物之形態使用之情形時,可於與二異氰酸酯反應前混合,亦可於使各聚酯多元醇單獨與二異氰酸酯反應而製成聚異氰酸酯後混合。 When polyester polyol (A) and polyester polyol (B) are used in combination, polyester polyol (A) and polyester polyol (B) may be used separately or in the form of a mixture. When used in the form of a mixture, they may be mixed before reacting with diisocyanate, or after reacting each polyester polyol with diisocyanate to prepare polyisocyanate.

即,作為聚異氰酸酯組合物之製造方法,例如可例舉以下方法等:使二異氰酸酯、聚酯多元醇(A)及聚酯多元醇(B)同時反應,獲得聚異氰酸酯組合物;將使二異氰酸酯與聚酯多元醇(A)反應所得者、與使二異氰酸酯與聚酯多元醇(B)反應所得者加以混合,獲得聚異氰酸酯組合物;使二異氰酸酯與聚酯多元醇(A)或聚酯多元醇(B)反應後,使殘留之聚酯多元醇進一步反應,獲得聚異氰酸酯組合物。 That is, as a method for producing a polyisocyanate composition, for example, the following methods can be cited: reacting diisocyanate, polyester polyol (A) and polyester polyol (B) simultaneously to obtain a polyisocyanate composition; mixing the product obtained by reacting diisocyanate with polyester polyol (A) and the product obtained by reacting diisocyanate with polyester polyol (B) to obtain a polyisocyanate composition; reacting diisocyanate with polyester polyol (A) or polyester polyol (B), and then further reacting the remaining polyester polyol to obtain a polyisocyanate composition.

反應時,二異氰酸酯之異氰酸基相對於聚酯多元醇(A)及聚酯多元醇(B)之羥基之莫耳比(異氰酸基/羥基之莫耳比)為1.5以上30以下,較佳為2.0以上25以下,更佳為2.1以上23以下,進而較佳為2.2以上20以下,進而較佳為2.3以上20.0以下,進而較佳為2.4以上20.0以下,進而較佳為2.5以上20.0以下,最佳為2.52以上20.0以下。 During the reaction, the molar ratio of the isocyanate group of the diisocyanate to the hydroxyl group of the polyester polyol (A) and the polyester polyol (B) (molar ratio of isocyanate group/hydroxyl group) is 1.5 to 30, preferably 2.0 to 25, more preferably 2.1 to 23, further preferably 2.2 to 20, further preferably 2.3 to 20.0, further preferably 2.4 to 20.0, further preferably 2.5 to 20.0, and most preferably 2.52 to 20.0.

聚酯多元醇與二異氰酸酯之反應係以如下方式進行。反應溫度通常為室溫(23℃左右)以上200℃以下,較佳為60℃以上180℃以下,較佳為60℃以上170℃以下。若反應溫度為上述下限值以上,則反應時間變得更 短,另一方面,若反應溫度為上述上限值以下,則能夠進一步避免不希望之由副反應所導致之聚異氰酸酯之黏度上升及凝膠化,亦能夠進一步避免生成之聚異氰酸酯之著色。 The reaction of polyester polyol and diisocyanate is carried out as follows. The reaction temperature is usually above room temperature (about 23°C) and below 200°C, preferably above 60°C and below 180°C, and preferably above 60°C and below 170°C. If the reaction temperature is above the lower limit, the reaction time becomes shorter. On the other hand, if the reaction temperature is below the upper limit, the undesirable viscosity increase and gelation of the polyisocyanate caused by the side reaction can be further avoided, and the coloring of the generated polyisocyanate can also be further avoided.

反應可於無溶劑之狀態下進行,亦可使用對異氰酸基惰性之任意溶劑進行。又,為了促進異氰酸基與羥基之反應,可視需要使用公知之觸媒。 The reaction can be carried out in the absence of a solvent, or using any solvent inert to isocyanate groups. In addition, in order to promote the reaction between isocyanate groups and hydroxyl groups, a known catalyst can be used as needed.

<聚異氰酸酯組合物之物性> <Physical properties of polyisocyanate composition>

本實施方式之聚異氰酸酯組合物之異氰酸基含有率(NCO基含有率)於實質上不包含溶劑或二異氰酸酯之狀態下,相對於聚異氰酸酯組合物之總質量,較佳為1.0質量%以上8.7質量%以下,更佳為1.5質量%以上8.6質量%以下,進而較佳為2.0質量%以上8.5質量%以下,進而較佳為2.5質量%以上8.5質量%以下,進而較佳為2.7質量%以上8.5質量%以下,尤佳為2.9質量%以上8.5質量%以下。 The isocyanate group content (NCO group content) of the polyisocyanate composition of the present embodiment is preferably 1.0 mass% to 8.7 mass% relative to the total mass of the polyisocyanate composition in a state where the solvent or diisocyanate is substantially not included, more preferably 1.5 mass% to 8.6 mass%, further preferably 2.0 mass% to 8.5 mass%, further preferably 2.5 mass% to 8.5 mass%, further preferably 2.7 mass% to 8.5 mass%, and particularly preferably 2.9 mass% to 8.5 mass%.

NCO基含有率例如可藉由使聚異氰酸酯組合物之異氰酸基與過量之胺(二丁胺等)發生反應,使用鹽酸等酸對殘留之胺進行反滴定而求出。 The NCO group content can be determined, for example, by reacting the isocyanate group of the polyisocyanate composition with an excess of amine (such as dibutylamine) and back-titrating the remaining amine with an acid such as hydrochloric acid.

本實施方式之聚異氰酸酯組合物之平均異氰酸基官能基數基於提昇黏著性樹脂組合物之硬化性及柔軟性之方面而言,較佳為2.0以上6.0以下,更佳為2.1以上5.9以下。 The average isocyanate functional group number of the polyisocyanate composition of this embodiment is preferably 2.0 to 6.0, and more preferably 2.1 to 5.9, in order to improve the curability and flexibility of the adhesive resin composition.

本實施方式之聚異氰酸酯組合物之平均異氰酸基官能基數可使用下述實施例中記載之方法進行測定。 The average isocyanate functional group number of the polyisocyanate composition of this embodiment can be measured using the method described in the following embodiment.

本實施方式之聚異氰酸酯組合物於用乙酸丁酯或乙酸乙酯等溶劑稀釋之情形時,基於調配等處理性之觀點而言,較佳為於23℃下為液體。 When the polyisocyanate composition of this embodiment is diluted with a solvent such as butyl acetate or ethyl acetate, it is preferably a liquid at 23°C from the perspective of handling such as formulation.

《硬化膜1》 《Hardening Film 1》

本實施方式之硬化膜1係使上述聚異氰酸酯組合物單獨硬化而成。 The cured film 1 of this embodiment is formed by curing the above-mentioned polyisocyanate composition alone.

本實施方式之硬化膜1之硬度較低,柔軟性及透明性良好。 The hardness of the cured film 1 of this embodiment is relatively low, and its softness and transparency are good.

本實施方式之硬化膜1例如可藉由以下而製造:將上述聚異氰酸酯組合物視需要用溶劑稀釋或溶解,使用塗佈機等塗敷於被黏著體上,視需要進行乾燥,並藉由熱進行硬化。 The cured film 1 of this embodiment can be manufactured, for example, by diluting or dissolving the above-mentioned polyisocyanate composition with a solvent as needed, applying it to the adherend using a coating machine, drying it as needed, and curing it by heat.

於本實施方式之硬化膜1為僅將上述聚異氰酸酯組合物塗敷於玻璃上並於23℃、65%濕度環境下保管168小時後,藉由空氣中之水分與上述聚異氰酸酯組合物之反應而形成之膜厚為40μm之硬化膜之情形時,23℃環境下之上述硬化膜之柯尼希硬度為60次以下,較佳為59次以下,更佳為58次以下。藉由使柯尼希硬度為上述上限值以下,硬度較低,柔軟性更優異。另一方面,上述硬化膜之柯尼希硬度之下限值並無特別限定,例如,可設為3次,可設為4次,亦可設為5次。 In the case where the cured film 1 of the present embodiment is a cured film with a thickness of 40 μm formed by the reaction of the moisture in the air with the polyisocyanate composition after the polyisocyanate composition is applied to the glass and stored in an environment of 23°C and 65% humidity for 168 hours, the Koenig hardness of the cured film in an environment of 23°C is 60 times or less, preferably 59 times or less, and more preferably 58 times or less. By making the Koenig hardness below the above upper limit, the hardness is lower and the softness is better. On the other hand, the lower limit of the Koenig hardness of the cured film is not particularly limited, for example, it can be set to 3 times, 4 times, or 5 times.

於本實施方式之硬化膜1為僅將上述聚異氰酸酯組合物塗敷於玻璃上並於23℃、65%濕度環境下保管168小時後,藉由空氣中之水分與上述聚 異氰酸酯組合物之反應而形成之膜厚為40μm之硬化膜之情形時,於將上述硬化膜貼附於霧度值為0.1%之玻璃上之狀態下藉由霧度計測定之霧度值較佳為3.0%以下,更佳為2.9%以下,進而較佳為2.8%以下。藉由使上述硬化膜之霧度值為上述上限值以下,透明性更優異。另一方面,上述硬化膜之霧度值之下限值並無特別限定,越接近0.0%越好,例如可設為0.0%,亦可設為0.05%。 In the case where the cured film 1 of the present embodiment is a cured film with a thickness of 40 μm formed by the reaction of the moisture in the air with the polyisocyanate composition after the polyisocyanate composition is applied to the glass and stored in an environment of 23°C and 65% humidity for 168 hours, the haze value measured by a haze meter when the cured film is attached to a glass with a haze value of 0.1% is preferably 3.0% or less, more preferably 2.9% or less, and further preferably 2.8% or less. By making the haze value of the cured film below the upper limit, the transparency is better. On the other hand, the lower limit of the haze value of the cured film is not particularly limited, and the closer to 0.0%, the better, for example, it can be set to 0.0% or 0.05%.

《硬化膜2》 《Hard Film 2》

上述聚異氰酸酯組合物亦可用作樹脂組合物之硬化劑成分。即,本實施方式之硬化膜2係使包含上述聚異氰酸酯組合物及多元醇(較佳為丙烯酸多元醇)之樹脂組合物硬化而成。上述硬化膜2例如可作為黏著劑層發揮功能。 The polyisocyanate composition can also be used as a curing agent component of the resin composition. That is, the cured film 2 of the present embodiment is formed by curing a resin composition comprising the polyisocyanate composition and a polyol (preferably an acrylic polyol). The cured film 2 can function as an adhesive layer, for example.

於上述樹脂組合物中,相對於多元醇100質量份,上述聚異氰酸酯組合物之含量較佳為0.01質量份以上200質量份以下,更佳為0.05質量份以上190質量份以下,進而較佳為0.10質量份以上180質量份以下。 In the above resin composition, relative to 100 parts by mass of the polyol, the content of the above polyisocyanate composition is preferably 0.01 parts by mass to 200 parts by mass, more preferably 0.05 parts by mass to 190 parts by mass, and further preferably 0.10 parts by mass to 180 parts by mass.

於上述樹脂組合物中,聚異氰酸酯組合物之異氰酸基相對於多元醇之羥基之莫耳比NCO/OH可根據所需之樹脂膜之物性決定,通常為0.01以上50以下。 In the above resin composition, the molar ratio NCO/OH of the isocyanate group of the polyisocyanate composition relative to the hydroxyl group of the polyol can be determined according to the desired physical properties of the resin film, and is usually above 0.01 and below 50.

於本實施方式之硬化膜2為使樹脂組合物於90℃下硬化30分鐘,並將其於23℃、65%濕度環境下保管168小時後形成之膜厚為40μm之硬化膜 之情形時,較佳為以夾具距離為20mm之方式將試驗片置於拉伸試驗機並以速度20mm/分鐘測定之拉伸試驗中之伸長率為140%以上,伸長率為140%時之應力為25.0MPa以下,且拉伸斷裂應力為上述伸長率為140%時之應力之1.2倍以上,上述樹脂組合物以上述聚異氰酸酯組合物之異氰酸基相對於上述多元醇之羥基之莫耳比NCO/OH為1之方式,包含上述聚異氰酸酯組合物及多元醇,上述多元醇之玻璃轉移溫度為0℃以上100℃以下,羥值為10mgKOH/g以上400mgKOH/g以下,且重量平均分子量為5.0×103以上×2.0×105以下,上述試驗片係將上述硬化膜切割成寬度10mm、長度100mm而成。 In the case where the cured film 2 of the present embodiment is a cured film having a thickness of 40 μm formed by curing the resin composition at 90° C. for 30 minutes and storing it at 23° C. and 65% humidity for 168 hours, it is preferred that the elongation in the tensile test measured at a speed of 20 mm/min by placing the test piece in a tensile tester with a clamp distance of 20 mm is 140% or more, the stress at the elongation of 140% is 25.0 MPa or less, and the tensile fracture is 100% or more. The cracking stress is 1.2 times or more of the stress when the elongation is 140%, the resin composition comprises the polyisocyanate composition and the polyol in such a manner that the molar ratio NCO/OH of the isocyanate group of the polyisocyanate composition to the hydroxyl group of the polyol is 1, the glass transition temperature of the polyol is 0° C. to 100° C., the hydroxyl value is 10 mgKOH/g to 400 mgKOH/g, and the weight average molecular weight is 5.0×10 3 to 2.0×10 5 , and the test piece is obtained by cutting the cured film into a piece with a width of 10 mm and a length of 100 mm.

又,上述伸長率較佳為140%以上,更佳為145%以上,進而較佳為150%以上,尤佳為155%以上,最佳為160%以上。另一方面,上述伸長率之上限例如可設為5000%。 Furthermore, the above elongation is preferably 140% or more, more preferably 145% or more, further preferably 150% or more, particularly preferably 155% or more, and most preferably 160% or more. On the other hand, the upper limit of the above elongation can be set to 5000%, for example.

又,上述伸長率為140%時之應力較佳為25.0MPa以下,更佳為24.0MPa以下,進而較佳為23.0MPa以下。另一方面,上述之上述伸長率為140%時之應力之下限例如可設為0.01MPa。 Furthermore, the stress when the elongation is 140% is preferably 25.0 MPa or less, more preferably 24.0 MPa or less, and further preferably 23.0 MPa or less. On the other hand, the lower limit of the stress when the elongation is 140% can be set to 0.01 MPa, for example.

又,拉伸斷裂應力較佳為上述伸長率為140%時之應力之1.2倍以上,更佳為1.3倍以上,進而更佳為1.4倍以上,進而較佳為1.5倍以上,進而更佳為1.6倍,尤佳為1.7倍。另一方面,拉伸斷裂應力相對於上述伸長率為140%時之應力之比之上限例如可設為30倍。 Furthermore, the tensile fracture stress is preferably 1.2 times or more of the stress at the above elongation of 140%, more preferably 1.3 times or more, further preferably 1.4 times or more, further preferably 1.5 times or more, further preferably 1.6 times, and particularly preferably 1.7 times. On the other hand, the upper limit of the ratio of the tensile fracture stress to the stress at the above elongation of 140% can be set to 30 times, for example.

藉由使上述伸長率為上述下限值以上,使上述伸長率為140%時之應 力為上述上限值以下,且使拉伸斷裂應力相對於上述伸長率為140%時之應力之比為上述下限值以上,硬化膜2之對被黏著體之追隨性、柔軟性、耐彎曲性、耐衝擊性、及耐久性更優異。 By making the elongation above the lower limit value or more, making the stress at the elongation of 140% below the upper limit value, and making the ratio of the tensile fracture stress to the stress at the elongation of 140% above the lower limit value, the cured film 2 has better tracking performance, flexibility, bending resistance, impact resistance, and durability to the adherend.

《黏著性樹脂組合物》 《Adhesive resin composition》

本實施方式之黏著性樹脂組合物包含上述聚異氰酸酯組合物、及玻璃轉移溫度為0.0℃以下之含有交聯性官能基之聚合物。 The adhesive resin composition of this embodiment includes the above-mentioned polyisocyanate composition and a polymer containing cross-linking functional groups with a glass transition temperature of 0.0°C or less.

本實施方式之黏著性樹脂組合物藉由包含上述聚異氰酸酯組合物,可形成柔軟性高於先前之黏著劑層,能夠獲得黏著力、保持力、硬化性、透明性、耐彎曲性、階差追隨性、耐衝擊性、及耐久性優異之黏著性樹脂片材。 The adhesive resin composition of this embodiment includes the above-mentioned polyisocyanate composition, which can form an adhesive layer with higher flexibility than the previous adhesive layer, and can obtain an adhesive resin sheet with excellent adhesion, retention, curability, transparency, bending resistance, step tracking, impact resistance, and durability.

其次,以下對本實施方式之黏著性樹脂組合物所包含之各成分詳細進行說明。 Next, the various components contained in the adhesive resin composition of this embodiment are described in detail below.

<含有交聯性官能基之聚合物> <Polymers containing cross-linking functional groups>

含有交聯性官能基之聚合物之玻璃轉移溫度為0.0℃以下,較佳為-75.0℃以上0.0℃以下,更佳為-75.0℃以上-5.0℃以下,進而較佳為-75.0℃以上-7.0℃以下,尤佳為-75.0℃以上-10.0℃以下。藉由使含有交聯性官能基之聚合物之玻璃轉移溫度Tg處於上述範圍內,黏著性樹脂組合物之硬化物之黏著力有變得更優異之趨勢。含有交聯性官能基之聚合物之玻璃轉移溫度例如可使用以下值,該值係對於使溶解或分散有含有交聯性官 能基之聚合物之溶液中之有機溶劑及水分於減壓下飛散後進行真空乾燥所得者,使用示差掃描熱量(DSC)測定裝置,於升溫速度5℃/分鐘之條件下進行測定所得。 The glass transition temperature of the polymer containing a crosslinking functional group is below 0.0°C, preferably -75.0°C to 0.0°C, more preferably -75.0°C to -5.0°C, further preferably -75.0°C to -7.0°C, and particularly preferably -75.0°C to -10.0°C. By making the glass transition temperature Tg of the polymer containing a crosslinking functional group within the above range, the adhesive resin composition tends to have a better adhesion. The glass transition temperature of a polymer containing a crosslinking functional group can be, for example, the following value, which is obtained by dispersing an organic solvent and water in a solution containing a polymer containing a crosslinking functional group under reduced pressure and then vacuum drying the solution, using a differential scanning calorimetry (DSC) measuring device at a temperature increase rate of 5°C/min.

含有交聯性官能基之聚合物之重量平均分子量Mw較佳為1.0×105以上5.0×106以下,更佳為1.5×105以上4.0×106以下,進而較佳為2.0×105以上3.0×106以下,尤佳為2.5×105以上2.5×106以下。藉由使含有交聯性官能基之聚合物之重量平均分子量處於上述範圍內,黏著性樹脂組合物之硬化物之黏著力、保持力、柔軟性、耐彎曲性、階差追隨性、耐衝擊性、及耐久性有變得更優異之趨勢。多元醇之重量平均分子量Mw例如可藉由下述實施例中記載之方法進行測定。 The weight average molecular weight Mw of the polymer containing a crosslinking functional group is preferably 1.0×10 5 to 5.0×10 6 , more preferably 1.5×10 5 to 4.0×10 6 , further preferably 2.0×10 5 to 3.0×10 6 , and particularly preferably 2.5×10 5 to 2.5×10 6. By making the weight average molecular weight of the polymer containing a crosslinking functional group within the above range, the adhesion, retention, flexibility, bending resistance, step tracking, impact resistance, and durability of the cured product of the adhesive resin composition tend to become better. The weight average molecular weight Mw of the polyol can be measured, for example, by the method described in the following examples.

作為含有交聯性官能基之聚合物,為含有可與上述聚異氰酸酯組合物之異氰酸基發生反應之交聯性官能基之聚合物即可。作為交聯性官能基,例如可例舉羥基、硫醇基、胺基、環氧基、氧雜環丁基、羧基、乙烯基、胺基等,其中,較佳為羥基、環氧基、羧基、乙烯基、或胺基,更佳為羥基、環氧基、氧雜環丁基、羧基、或胺基,進而較佳為羥基、羧基、胺基,尤佳為羥基。即,作為含有交聯性官能基之聚合物,較佳為多元醇。 As a polymer containing a crosslinking functional group, it is sufficient to be a polymer containing a crosslinking functional group that can react with the isocyanate group of the above-mentioned polyisocyanate composition. As a crosslinking functional group, for example, a hydroxyl group, a thiol group, an amino group, an epoxy group, an oxycyclobutyl group, a carboxyl group, a vinyl group, an amino group, etc. can be cited, among which a hydroxyl group, an epoxy group, a carboxyl group, a vinyl group, or an amino group is preferred, a hydroxyl group, an epoxy group, an oxycyclobutyl group, a carboxyl group, or an amino group is more preferred, a hydroxyl group, a carboxyl group, an amino group is further preferred, and a hydroxyl group is particularly preferred. That is, as a polymer containing a crosslinking functional group, a polyol is preferred.

作為含有交聯性官能基之聚合物,具體而言,例如可例舉脂肪族烴多元醇、聚醚多元醇、聚酯多元醇、環氧樹脂、含氟多元醇、丙烯酸系聚合物、胺基甲酸酯系聚合物等。 Specific examples of polymers containing crosslinking functional groups include aliphatic hydrocarbon polyols, polyether polyols, polyester polyols, epoxy resins, fluorine-containing polyols, acrylic polymers, and urethane polymers.

其中,作為含有交聯性官能基之聚合物,較佳為丙烯酸系聚合物或 胺基甲酸酯系聚合物。 Among them, the polymer containing a cross-linking functional group is preferably an acrylic polymer or a urethane polymer.

[脂肪族烴多元醇] [Aliphatic polyols]

作為上述脂肪族烴多元醇,例如可例舉末端羥基化聚丁二烯或其氫化物等。 Examples of the above-mentioned aliphatic hydrocarbon polyols include terminal hydroxylated polybutadiene or its hydrogenated product.

[聚醚多元醇] [Polyether polyol]

作為上述聚醚多元醇,例如可例舉使用以下(1)~(3)中之任一種方法等所得者。 As the above-mentioned polyether polyol, for example, one obtained by any of the following methods (1) to (3) can be cited.

(1)使單獨之環氧烷或環氧烷之混合物加成於單獨之多元醇或多元醇之混合物所得之聚醚多元醇或聚四亞甲基醚二醇。 (1) Polyether polyol or polytetramethylene ether glycol obtained by adding a single alkylene oxide or a mixture of alkylene oxides to a single polyol or a mixture of polyols.

(2)使多官能化合物與環氧烷反應所得之聚醚多元醇。 (2) Polyether polyols obtained by reacting multifunctional compounds with alkylene oxides.

(3)以(1)或(2)中所得之聚醚多元醇作為介質,使丙烯醯胺等聚合所得之所謂聚合物多元醇。 (3) The so-called polymer polyol obtained by polymerizing acrylamide etc. using the polyether polyol obtained in (1) or (2) as a medium.

作為上述多元醇,例如可例舉甘油或丙二醇等。 Examples of the above-mentioned polyols include glycerin and propylene glycol.

作為上述環氧烷,例如可例舉環氧乙烷、環氧丙烷等。 Examples of the above-mentioned alkylene oxides include ethylene oxide, propylene oxide, etc.

作為上述多官能化合物,例如可例舉乙二胺、乙醇胺等。 Examples of the above-mentioned multifunctional compounds include ethylenediamine, ethanolamine, etc.

[聚酯多元醇] [Polyester polyol]

作為上述聚酯多元醇,例如可例舉以下(1)或(2)中之任一種聚酯多元醇。 As the above-mentioned polyester polyol, for example, any one of the following (1) or (2) polyester polyols can be cited.

(1)藉由單獨之二元酸或2種以上二元酸之混合物、與單獨之多元醇或2種以上多元醇之混合物之縮合反應所得之聚酯多元醇樹脂。 (1) A polyester polyol resin obtained by the condensation reaction of a single dibasic acid or a mixture of two or more dibasic acids with a single polyol or a mixture of two or more polyols.

(2)使ε-己內酯藉由多元醇進行開環聚合所得之聚己內酯多元醇。 (2) Polycaprolactone polyol obtained by ring-opening polymerization of ε-caprolactone with polyol.

作為上述二元酸,例如,可例舉琥珀酸、己二酸、二聚酸、馬來酸酐、鄰苯二甲酸酐、間苯二甲酸、對苯二甲酸、1,4-環己烷二羧酸等羧酸等。 Examples of the above-mentioned dibasic acid include succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid and other carboxylic acids.

作為上述多元醇,例如,可例舉乙二醇、丙二醇、二乙二醇、1,4-丁二醇、新戊二醇、1,6-己二醇、三甲基戊二醇、環己二醇、三羥甲基丙烷、甘油、季戊四醇、2-羥甲基丙二醇、乙氧化三羥甲基丙烷等。 Examples of the above-mentioned polyols include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trihydroxymethylpropane, glycerin, pentaerythritol, 2-hydroxymethylpropanediol, and ethoxylated trihydroxymethylpropane.

[環氧樹脂] [Epoxy resin]

作為上述環氧樹脂,例如,可例舉酚醛清漆型環氧樹脂、β-甲基表氯醇型環氧樹脂、環狀環氧乙烷型環氧樹脂、縮水甘油醚型環氧樹脂、二醇醚型環氧樹脂、環氧型脂肪族不飽和化合物、環氧化脂肪酸酯、酯型多元羧酸、胺基縮水甘油基型環氧樹脂、鹵化型環氧樹脂、間苯二酚型環氧樹脂等環氧樹脂、及使該等環氧樹脂藉由胺基化合物、聚醯胺化合物等改性所得之樹脂等。 Examples of the epoxy resin include novolac epoxy resin, β-methyl epichlorohydrin epoxy resin, epoxy ethylene oxide type epoxy resin, glycidyl ether epoxy resin, glycol ether epoxy resin, epoxy aliphatic unsaturated compound, epoxidized fatty acid ester, ester polycarboxylic acid, amino glycidyl epoxy resin, halogenated epoxy resin, resorcinol epoxy resin, and epoxy resins obtained by modifying the epoxy resins with amino compounds, polyamide compounds, and the like.

[含氟多元醇] [Fluorinated polyols]

作為上述含氟多元醇,例如,可例舉參考文獻1(日本專利特開昭57-34107號公報)、參考文獻2(日本專利特開昭61-275311號公報)等中揭示之氟烯烴、環己基乙烯基醚、羥烷基乙烯基醚、單羧酸乙烯酯等共聚物等。 As the above-mentioned fluorine-containing polyol, for example, there can be cited copolymers of fluoroolefins, cyclohexyl vinyl ether, hydroxyalkyl vinyl ether, monocarboxylic acid vinyl esters, etc. disclosed in Reference 1 (Japanese Patent Publication No. 57-34107), Reference 2 (Japanese Patent Publication No. 61-275311), etc.

[丙烯酸系聚合物] [Acrylic polymer]

上述丙烯酸系聚合物包含1種以上之具有交聯性官能基之聚合性(甲 基)丙烯酸單體單元。作為交聯性官能基,較佳為包含羥基、羧基、環氧基、或乙烯基,更佳為包含羥基或羧基,進而較佳為包含羥基。 The acrylic polymer contains one or more polymerizable (meth) acrylic monomer units having a cross-linking functional group. As the cross-linking functional group, it is preferred to contain a hydroxyl group, a carboxyl group, an epoxy group, or a vinyl group, more preferably a hydroxyl group or a carboxyl group, and further preferably a hydroxyl group.

丙烯酸系聚合物可單獨包含交聯性官能基,亦可組合包含2種以上不同種類之交聯性官能基。即,丙烯酸系聚合物可為使具有交聯性官能基之聚合性(甲基)丙烯酸單體單獨聚合而成者,亦可為使2種以上具有不同種類之交聯性官能基之聚合性(甲基)丙烯酸單體組合共聚而成者。 The acrylic polymer may contain a crosslinking functional group alone or in combination of two or more different types of crosslinking functional groups. That is, the acrylic polymer may be obtained by polymerizing a polymerizable (meth) acrylic monomer having a crosslinking functional group alone or by copolymerizing two or more polymerizable (meth) acrylic monomers having different types of crosslinking functional groups in combination.

丙烯酸系聚合物除具有交聯性官能基之聚合性(甲基)丙烯酸單體單元以外,可包含1種以上不具有交聯性官能基之聚合性(甲基)丙烯酸單體單元。 In addition to the polymerizable (meth)acrylic monomer units having a cross-linking functional group, the acrylic polymer may contain one or more polymerizable (meth)acrylic monomer units not having a cross-linking functional group.

即,丙烯酸系聚合物係藉由使1種以上具有交聯性官能基之聚合性(甲基)丙烯酸單體聚合而得,或者藉由使1種以上具有交聯性官能基之聚合性(甲基)丙烯酸單體與1種以上不具有交聯性官能基之聚合性(甲基)丙烯酸單體共聚而得。 That is, the acrylic polymer is obtained by polymerizing one or more polymerizable (meth) acrylic monomers having a crosslinking functional group, or by copolymerizing one or more polymerizable (meth) acrylic monomers having a crosslinking functional group with one or more polymerizable (meth) acrylic monomers not having a crosslinking functional group.

丙烯酸系聚合物較佳為除具有交聯性官能基之聚合性(甲基)丙烯酸系單體單元以外,包含1種以上酯基末端之碳數為1以上18以下之(甲基)丙烯酸酯單體單元。 The acrylic polymer preferably contains, in addition to the polymerizable (meth) acrylic monomer unit having a cross-linking functional group, one or more (meth) acrylic ester monomer units having a carbon number of 1 to 18 at the end of the ester group.

即,丙烯酸系聚合物可為使1種以上具有交聯性官能基之聚合性(甲基)丙烯酸系單體與1種以上酯基末端之碳數為1以上18以下之(甲基)丙烯酸酯單體共聚而成者。(甲基)丙烯酸酯單體可具有交聯性官能基,亦可不具有交聯性官能基,較佳為不具有交聯性官能基。 That is, the acrylic polymer may be obtained by copolymerizing one or more polymerizable (meth) acrylic monomers having a crosslinking functional group and one or more (meth) acrylic ester monomers having a carbon number of 1 to 18 at the end of the ester group. The (meth) acrylic ester monomer may or may not have a crosslinking functional group, preferably not having a crosslinking functional group.

作為(甲基)丙烯酸酯單體所具有之酯基末端之碳數,較佳為1以上18以下。 The number of carbon atoms at the end of the ester group of the (meth)acrylate monomer is preferably 1 or more and 18 or less.

作為上述具有交聯性官能基之聚合性(甲基)丙烯酸系單體,例如可例舉以下(i)~(v)所示者。該等可單獨使用1種,亦可將2種以上組合使用。 As the above-mentioned polymerizable (meth) acrylic monomers having crosslinking functional groups, for example, those shown in (i) to (v) below can be cited. These can be used alone or in combination of two or more.

(i)丙烯酸-2-羥基乙酯、丙烯酸-2-羥基丙酯、丙烯酸-2-羥基丁酯、丙烯酸-4-羥基丁酯、丙烯酸-6-羥基己酯、丙烯酸-8-羥基辛酯等具有羥基之丙烯酸酯類。 (i) Acrylic acid esters having a hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, and 8-hydroxyoctyl acrylate.

(ii)甲基丙烯酸-2-羥基乙酯、甲基丙烯酸-2-羥基丙酯、甲基丙烯酸-2-羥基丁酯、甲基丙烯酸-4-羥基丁酯、甲基丙烯酸-6-羥基己酯、甲基丙烯酸-8-羥基辛酯等具有羥基之甲基丙烯酸酯類。 (ii) Methacrylates having a hydroxyl group such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate, and 8-hydroxyoctyl methacrylate.

(iii)甘油之丙烯酸單酯或甲基丙烯酸單酯、三羥甲基丙烷之丙烯酸單酯或甲基丙烯酸單酯等具有多元羥基之(甲基)丙烯酸酯類。 (iii) (Meth)acrylates with polyhydroxyl groups, such as glycerol monoacrylate or methacrylate, trihydroxymethylpropane monoacrylate or methacrylate.

(iv)丙烯酸、甲基丙烯酸等不飽和羧酸。 (iv) Unsaturated carboxylic acids such as acrylic acid and methacrylic acid.

(v)甲基丙烯酸縮水甘油酯等具有環氧基之(甲基)丙烯酸酯類。 (v) (Meth)acrylates with epoxy groups such as glycidyl methacrylate.

作為酯基末端之碳數為1以上18以下之(甲基)丙烯酸酯單體,例如,可例舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲 基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸環己酯等(甲基)丙烯酸酯類等。該等可單獨使用1種,亦可將2種以上組合使用。 Examples of the (meth)acrylate monomer having a carbon number of 1 to 18 at the end of the ester group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, and octyl (meth)acrylate. (Meth)acrylates such as isononyl acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, benzyl (meth)acrylate, and cyclohexyl (meth)acrylate. These may be used alone or in combination of two or more.

丙烯酸系聚合物除具有交聯性官能基之聚合性(甲基)丙烯酸系單體單元以外,可進而包含除上述(甲基)丙烯酸酯單體以外之其他單體單元。 In addition to the polymerizable (meth)acrylic monomer units having cross-linking functional groups, the acrylic polymer may further include other monomer units other than the above-mentioned (meth)acrylate monomers.

即,丙烯酸系聚合物係藉由使1種以上具有交聯性官能基之聚合性(甲基)丙烯酸系單體聚合而得,或者藉由使1種以上具有交聯性官能基之聚合性(甲基)丙烯酸系單體與1種以上其他單體共聚而得。其他單體可具有交聯性官能基,亦可不具有交聯性官能基,較佳為不具有交聯性官能基。 That is, the acrylic polymer is obtained by polymerizing one or more polymerizable (meth) acrylic monomers having a crosslinking functional group, or by copolymerizing one or more polymerizable (meth) acrylic monomers having a crosslinking functional group with one or more other monomers. The other monomers may or may not have a crosslinking functional group, preferably not having a crosslinking functional group.

作為其他單體,例如可例舉以下(i)~(ii)所示者等。該等可單獨使用1種,亦可將2種以上組合使用。 As other monomers, for example, those shown in the following (i) to (ii) can be cited. These can be used alone or in combination of two or more.

(i)(甲基)丙烯醯胺、N-羥甲基丙烯醯胺、二丙酮丙烯醯胺、二甲胺基丙基丙烯醯胺等不飽和醯胺。 (i) Unsaturated amides such as (methyl)acrylamide, N-hydroxymethylacrylamide, diacetoneacrylamide, dimethylaminopropylacrylamide, etc.

(ii)苯乙烯、乙烯基甲苯、乙酸乙烯酯、(甲基)丙烯腈、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺、丙烯醯

Figure 111129090-A0305-02-0028-8
啉、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯。 (ii) Styrene, vinyl toluene, vinyl acetate, (meth)acrylonitrile, N-vinyl pyrrolidone, N-vinyl caprolactam, acrylamide
Figure 111129090-A0305-02-0028-8
phenoxyethylene, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate.

進而,作為可與上述具有交聯性官能基之聚合性(甲基)丙烯酸系單體共聚之其他單體,可使用日本專利特開平1-261409號公報(參考文獻3)及 日本專利特開平3-006273號公報(參考文獻4)等中揭示之聚合性紫外線穩定性單體。 Furthermore, as other monomers copolymerizable with the above-mentioned polymerizable (meth) acrylic monomers having a crosslinking functional group, polymerizable ultraviolet-stable monomers disclosed in Japanese Patent Laid-Open No. 1-261409 (reference 3) and Japanese Patent Laid-Open No. 3-006273 (reference 4) can be used.

作為上述聚合性紫外線穩定性單體,具體而言,例如可例舉4-(甲基)丙烯醯氧基-2、2、6、6-四甲基哌啶、4-(甲基)丙烯醯基胺基-2、2、6、6-四甲基哌啶、1-巴豆醯基-4-巴豆醯氧基-2、2、6、6-四甲基哌啶、2-羥基-4-(3-甲基丙烯醯氧基-2-羥基丙氧基)二苯甲酮等。 Specific examples of the above-mentioned polymerizable ultraviolet-stable monomer include 4-(methyl)acryloyloxy-2, 2, 6, 6-tetramethylpiperidine, 4-(methyl)acryloylamino-2, 2, 6, 6-tetramethylpiperidine, 1-crotonyl-4-crotonyloxy-2, 2, 6, 6-tetramethylpiperidine, and 2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropoxy)benzophenone.

例如,藉由使上述單體成分於公知之過氧化物或偶氮化合物等自由基聚合起始劑之存在下進行溶液聚合,並視需要用有機溶劑等稀釋,能夠獲得丙烯酸系聚合物。 For example, by subjecting the above-mentioned monomer components to solution polymerization in the presence of a known free radical polymerization initiator such as a peroxide or azo compound, and diluting with an organic solvent as needed, an acrylic polymer can be obtained.

於獲得水系基質之丙烯酸系聚合物之情形時,可藉由使烯烴性不飽和化合物進行溶液聚合而轉化成水層之方法、或乳化聚合等公知之方法而製造。於該情形時,藉由使用胺或氨中和含有丙烯酸、甲基丙烯酸等羧酸之單體或含磺酸單體等之酸性部分,可賦予水溶性或水分散性。 When obtaining an acrylic polymer with a water-based matrix, it can be produced by a method of converting an olefinic unsaturated compound into a water layer by solution polymerization or by a known method such as emulsion polymerization. In this case, the acidic part of the monomer containing carboxylic acid such as acrylic acid and methacrylic acid or the monomer containing sulfonic acid can be neutralized with amine or ammonia to give water solubility or water dispersibility.

[與硬化劑成分之含量比] [Ratio of content to hardener component]

於本實施方式之黏著性樹脂組合物中,相對於含有交聯性官能基之聚合物100質量份,上述聚異氰酸酯組合物之含量較佳為0.01質量份以上20.00質量份以下,更佳為0.03質量份以上15.00質量份以下,進而較佳為0.05質量份以上13.0質量份以下。 In the adhesive resin composition of the present embodiment, the content of the polyisocyanate composition is preferably 0.01 to 20.00 parts by mass, more preferably 0.03 to 15.00 parts by mass, and further preferably 0.05 to 13.0 parts by mass, relative to 100 parts by mass of the polymer containing the crosslinking functional group.

<其他成分> <Other ingredients>

本實施方式之黏著性樹脂組合物可進而包含其他添加劑。 The adhesive resin composition of this embodiment may further include other additives.

作為其他添加劑,例如,可例舉可與含有交聯性官能基之聚合物發生反應之除聚異氰酸酯組合物以外之硬化劑、硬化觸媒、溶劑、顏料類(體質顏料、著色顏料、金屬顏料等)、黏著賦予樹脂、光聚合起始劑、紫外線吸收劑、光穩定劑、自由基穩定劑、抑制烘烤步驟時之著色之抗黃變劑、塗面調整劑、流動調整劑、顏料分散劑、消泡劑、增黏劑、造膜助劑等。 As other additives, for example, hardeners other than polyisocyanate compositions that can react with polymers containing crosslinking functional groups, hardening catalysts, solvents, pigments (physical pigments, coloring pigments, metal pigments, etc.), adhesion-imparting resins, photopolymerization initiators, ultraviolet light absorbers, light stabilizers, free radical stabilizers, anti-yellowing agents that inhibit coloring during the baking step, coating conditioners, flow conditioners, pigment dispersants, defoamers, thickeners, film-forming aids, etc. can be cited.

作為上述硬化劑,例如,可例舉三聚氰胺樹脂、尿素樹脂、含環氧基化合物或樹脂、含羧基化合物或樹脂、酸酐、含烷氧基矽烷基化合物或樹脂、醯肼化合物等。 Examples of the above-mentioned hardener include melamine resins, urea resins, epoxy-containing compounds or resins, carboxyl-containing compounds or resins, acid anhydrides, alkoxysilane-containing compounds or resins, hydrazide compounds, etc.

作為上述硬化觸媒,可為鹼性化合物,亦可為路易斯酸性化合物。 The above-mentioned hardening catalyst may be an alkaline compound or a Lewis acid compound.

作為上述鹼性化合物,例如,可例舉金屬氫氧化物、金屬烷氧化物、金屬羧酸鹽、乙醯丙酮金屬鹽、鎓鹽之氫氧化物、羧酸鎓鹽、鎓鹽之鹵化物、活性亞甲基系化合物之金屬鹽、活性亞甲基系化合物之鎓鹽、胺基矽烷類、胺類、膦類等。作為上述鎓鹽,較佳為銨鹽、鏻鹽或鋶鹽。 As the above-mentioned alkaline compound, for example, metal hydroxides, metal alkoxides, metal carboxylates, metal acetylacetonate, hydroxides of onium salts, onium carboxylates, halides of onium salts, metal salts of active methylene compounds, onium salts of active methylene compounds, aminosilanes, amines, phosphines, etc. As the above-mentioned onium salt, ammonium salts, phosphonium salts or cobalt salts are preferred.

作為上述路易斯酸性化合物,例如可例舉有機錫化合物、有機鋅化合物、有機鈦化合物、有機鋯化合物等。 Examples of the above-mentioned Lewis acidic compounds include organic tin compounds, organic zinc compounds, organic titanium compounds, organic zirconium compounds, etc.

作為上述溶劑,例如,可例舉1-甲基吡咯啶酮、乙二醇單乙醚、二乙二醇單乙醚、乙二醇單甲醚、二乙二醇單甲醚、二丙二醇單甲醚、丙二 醇單甲醚、3-甲氧基-3-甲基-1-丁醇、乙二醇二乙醚、二乙二醇二乙醚、乙二醇二甲醚、二乙二醇二甲醚、二丙二醇二甲醚(DPDM)、丙二醇二甲醚、甲基乙基酮、丙酮、甲基異丁基酮、丙二醇單甲醚乙酸酯、乙醇、甲醇、異丙醇、1-丙醇、異丁醇、1-丁醇、第三丁醇、2-乙基己醇、環己醇、乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、1,4-丁二醇、1,3-丁二醇、乙酸乙酯、乙酸異丙酯、乙酸丁酯、甲苯、二甲苯、戊烷、異戊烷、己烷、異己烷、環己烷、溶劑石腦油、礦油精等。該等溶劑可單獨使用1種,亦可將2種以上組合使用。 Examples of the solvent include 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether (DPDM), propylene glycol dimethyl ether, methyl ethyl ketone, acetone, methyl Isobutyl ketone, propylene glycol monomethyl ether acetate, ethanol, methanol, isopropyl alcohol, 1-propanol, isobutyl alcohol, 1-butanol, tert-butyl alcohol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, isopentane, hexane, isohexane, cyclohexane, solvent naphtha, mineral spirits, etc. These solvents may be used alone or in combination of two or more.

又,作為顏料類(體質顏料、著色顏料、金屬顏料等)、紫外線吸收劑、光穩定劑、自由基穩定劑、抑制烘烤步驟時之著色之抗黃變劑、塗面調整劑、流動調整劑、顏料分散劑、消泡劑、增黏劑及造膜助劑,可適當選擇公知者來使用。 In addition, as pigments (physical pigments, coloring pigments, metal pigments, etc.), ultraviolet absorbers, light stabilizers, free radical stabilizers, anti-yellowing agents for inhibiting coloring during the baking step, coating conditioners, flow conditioners, pigment dispersants, defoamers, thickeners and film-forming aids, known ones can be appropriately selected for use.

<黏著性樹脂組合物之製造方法> <Method for producing adhesive resin composition>

黏著性樹脂組合物可藉由先前公知之方法製造。例如,可使用利用班布里混合機、單螺桿擠出機、雙螺桿擠出機、雙向捏合機、多螺桿擠出機等普通混合機之熔融混練方法,使各成分溶解或分散混合後藉由塗佈機等塗敷於劃痕膜後加熱去除溶劑之方法等。 The adhesive resin composition can be manufactured by a previously known method. For example, a melt kneading method using a Banbury mixer, a single-screw extruder, a twin-screw extruder, a bidirectional kneader, a multi-screw extruder, etc. can be used to dissolve or disperse the components and then apply them to the scratch film by a coating machine, etc., and then heat to remove the solvent.

為了實現輕量化、柔軟化、密接性之提昇效果,本實施方式之黏著性樹脂組合物可發泡。作為發泡方法,有化學方法、物理方法、熱膨脹型微球之使用等。分別可藉由無機系發泡劑或有機系發泡劑等化學發泡劑或 物理發泡劑等之添加、或者熱膨脹型微球之添加等,使氣泡分佈於材料內部。 In order to achieve the effects of lightening, softening, and improving adhesion, the adhesive resin composition of this embodiment can be foamed. As the foaming method, there are chemical methods, physical methods, and the use of thermal expansion microspheres. Bubbles can be distributed inside the material by adding chemical foaming agents such as inorganic foaming agents or organic foaming agents, physical foaming agents, etc., or adding thermal expansion microspheres.

又,藉由添加中空填料(已膨脹球),可實現輕量化、柔軟化、密接性之提昇。 In addition, by adding hollow fillers (expanded balls), it is possible to achieve weight reduction, flexibility, and improved adhesion.

為了調整黏著力,本實施方式之黏著性樹脂組合物可添加黏著賦予樹脂。作為黏著賦予樹脂,例如,可例舉松香系黏著賦予樹脂、萜烯系黏著賦予樹脂、石油系黏著賦予樹脂、苯乙烯系黏著賦予樹脂等。該等黏著賦予樹脂可單獨使用1種,亦可將2種以上組合使用。又,黏著賦予樹脂之軟化點較佳為90℃以上160℃以下。 In order to adjust the adhesive force, the adhesive resin composition of the present embodiment may be added with an adhesive-imparting resin. As the adhesive-imparting resin, for example, rosin-based adhesive-imparting resins, terpene-based adhesive-imparting resins, petroleum-based adhesive-imparting resins, styrene-based adhesive-imparting resins, etc. may be cited. Such adhesive-imparting resins may be used alone or in combination of two or more. In addition, the softening point of the adhesive-imparting resin is preferably above 90°C and below 160°C.

《黏著性樹脂片材》 《Adhesive resin sheet》

本實施方式之黏著性樹脂片材係使上述黏著性樹脂組合物藉由熱或光發生硬化而成。 The adhesive resin sheet of this embodiment is formed by hardening the above-mentioned adhesive resin composition by heat or light.

本實施方式之黏著性樹脂片材之黏著性、耐彎曲性、保持力、硬化性、階差追隨性、耐衝擊性、耐久性、及透明性優異。 The adhesive resin sheet of this embodiment has excellent adhesion, bending resistance, holding power, curability, step tracking, impact resistance, durability, and transparency.

作為本實施方式之黏著性樹脂片材(黏著劑層)之厚度,可根據使用之用途適當決定,較佳為1μm以上1000μm以下,更佳為2μm以上900μm以下,進而較佳為3μm以上800μm以下,尤佳為5μm以上700μm以下。 The thickness of the adhesive resin sheet (adhesive layer) of this embodiment can be appropriately determined according to the intended use, preferably 1 μm to 1000 μm, more preferably 2 μm to 900 μm, further preferably 3 μm to 800 μm, and particularly preferably 5 μm to 700 μm.

本實施方式之黏著性樹脂片材例如可藉由將黏著性樹脂組合物塗敷 於基材上,視需要進行乾燥,其後進行硬化而製造。 The adhesive resin sheet of the present embodiment can be manufactured, for example, by applying the adhesive resin composition to a substrate, drying it as needed, and then hardening it.

作為將黏著性樹脂組合物塗敷於基材上之方法,例如,可例舉使用塗敷器、輥式塗佈機、刮刀塗佈機、凹版塗佈機等塗佈之方法。於上述塗敷後進行乾燥之情形時,例如,可例舉將所得之積層體置於乾燥機等,例如於50℃以上150℃以下之溫度下乾燥1分鐘以上30分鐘以下之加熱乾燥方法。或者,作為其他乾燥方法,例如可例舉自然乾燥、熱風乾燥、紅外線乾燥等。 As a method of applying the adhesive resin composition to the substrate, for example, a coating method using an applicator, a roller coater, a doctor blade coater, a gravure coater, etc. can be cited. In the case of drying after the above coating, for example, a heat drying method of placing the obtained laminate in a dryer, for example, at a temperature of 50°C to 150°C for 1 minute to 30 minutes can be cited. Alternatively, as other drying methods, for example, natural drying, hot air drying, infrared drying, etc. can be cited.

作為基材,並無特別限定,例如,可例示:高級紙、塗料紙、光塗料紙、熱敏紙、噴墨紙等紙;織布、不織布等布;聚氯乙烯、合成紙、聚對苯二甲酸乙二酯(PET)、聚丙烯、聚乙烯、三乙酸纖維素、二乙酸纖維素、聚苯乙烯、聚碳酸酯、尼龍、聚乙烯醇、乙烯-乙酸乙烯酯共聚物、聚醯亞胺等樹脂膜;多孔質聚丙烯膜等多孔質樹脂膜;對PET、聚烯烴等進行鋁等之金屬蒸鍍所得之蒸鍍膜;金屬箔等。作為基材,可為表面實施剝離處理者。 The substrate is not particularly limited, and examples thereof include: high-grade paper, coated paper, glossy coated paper, thermal paper, inkjet paper, etc.; woven fabrics, non-woven fabrics, etc.; resin films such as polyvinyl chloride, synthetic paper, polyethylene terephthalate (PET), polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, polystyrene, polycarbonate, nylon, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyimide, etc.; porous resin films such as porous polypropylene films; evaporated films obtained by evaporating metals such as aluminum on PET, polyolefins, etc.; metal foils, etc. The substrate may be one that has been subjected to a peeling treatment on the surface.

作為硬化時之加熱溫度,可設為70℃以上160℃以下,可設為75℃以上155℃以下,亦可設為80℃以上150℃以下。 The heating temperature during hardening can be set to be above 70℃ and below 160℃, above 75℃ and below 155℃, or above 80℃ and below 150℃.

關於本實施方式之黏著性樹脂片材,凝膠分率較佳為20.0質量%以上99.9質量%以下,更佳為25.0質量%以上99.9質量%以下,進而較佳為30.0質量%以上99.9質量%以下,尤佳為32.0質量%以上99.9質量%以下,最佳為35.0質量%以上99.9質量%以下,上述凝膠分率係藉由對於自具備 厚度50μm之黏著性樹脂片材之積層體剝離上述經剝離處理之聚對苯二甲酸乙二酯膜所得之上述黏著性樹脂片材,於23℃、50%RH環境下保管7天後,用網狀片材包裹,於乙酸乙酯中於23℃下浸漬1週,取出後,於120℃下乾燥2小時而算出,該厚度50μm之黏著性樹脂片材係將上述黏著性樹脂組合物塗敷於厚度38μm之經剝離處理之聚對苯二甲酸乙二酯膜上,於135℃下乾燥3分鐘使其硬化後,於23℃、50%RH環境下保管7天所得。藉由使凝膠分率為上述下限值以上,黏著力、保持力、耐久性、耐彎曲性、及硬化性更優異。 Regarding the adhesive resin sheet of the present embodiment, the gel fraction is preferably 20.0 mass % to 99.9 mass %, more preferably 25.0 mass % to 99.9 mass %, further preferably 30.0 mass % to 99.9 mass %, particularly preferably 32.0 mass % to 99.9 mass %, and most preferably 35.0 mass % to 99.9 mass %. The gel fraction is obtained by peeling off the above-exfoliated polymer from a laminate of an adhesive resin sheet having a thickness of 50 μm. The above-mentioned adhesive resin sheet obtained from the polyethylene terephthalate film was stored in an environment of 23°C and 50% RH for 7 days, then wrapped with a mesh sheet, immersed in ethyl acetate at 23°C for 1 week, taken out, and dried at 120°C for 2 hours. The 50μm thick adhesive resin sheet was obtained by applying the above-mentioned adhesive resin composition on a 38μm thick polyethylene terephthalate film that had been peeled, drying it at 135°C for 3 minutes to harden it, and then storing it at 23°C and 50% RH for 7 days. By making the gel fraction above the above lower limit, the adhesion, retention, durability, bending resistance, and hardening properties are more excellent.

再者,此處所說之凝膠分率係浸漬於乙酸乙酯後進行乾燥之上述黏著性樹脂片材之質量相對於浸漬於乙酸乙酯前之上述黏著性樹脂片材之質量之百分率。 Furthermore, the gel fraction mentioned here is the percentage of the mass of the above-mentioned adhesive resin sheet after being immersed in ethyl acetate and then dried relative to the mass of the above-mentioned adhesive resin sheet before being immersed in ethyl acetate.

關於本實施方式之黏著性樹脂片材,180度剝離黏著力較佳為0.05N/20mm以上65.00N/20mm以下,更佳為0.05N/20mm以上64.50N/20mm以下,進而較佳為0.05N/20mm以上64.00N/20mm以下,尤佳為0.05N/20mm以上63.50N/20mm以下,最佳為0.05N/20mm以上63.00N/20mm以下,該180度剝離黏著力係將具備厚度50μm、寬度20mm及長度100mm之黏著性樹脂片材之積層體貼附於作為被黏著體之SUS304BA板上,使用2kg輥進行1次往復壓接,於23℃下固化30分鐘後,於23℃下以300mm/分鐘之速度測得,該厚度50μm、寬度20mm及長度100mm之黏著性樹脂片材係將上述黏著性樹脂組合物塗敷於厚度25μm之聚對苯二甲酸乙二酯膜上,於135℃下乾燥3分鐘使其硬化後,於23℃、50%RH環境下保管7天所得。藉由使180度剝離黏著力為上述下限值以上,黏著力 更優異。 Regarding the adhesive resin sheet of the present embodiment, the 180-degree peeling adhesion is preferably 0.05N/20mm to 65.00N/20mm, more preferably 0.05N/20mm to 64.50N/20mm, further preferably 0.05N/20mm to 64.00N/20mm, particularly preferably 0.05N/20mm to 63.50N/20mm, and most preferably 0.05N/20mm to 63.00N/20mm. The 180-degree peeling adhesion is for a sheet having a thickness of 50μm and a width of The laminate of the adhesive resin sheet with a thickness of 20 mm and a length of 100 mm was attached to the SUS304BA plate as the adherend, and a 2kg roller was used for one reciprocating press bonding. After curing at 23°C for 30 minutes, the adhesive resin sheet with a thickness of 50 μm, a width of 20 mm and a length of 100 mm was measured at a speed of 300 mm/min at 23°C. The adhesive resin composition was applied to a polyethylene terephthalate film with a thickness of 25 μm, dried at 135°C for 3 minutes to harden, and then stored at 23°C and 50% RH for 7 days. By making the 180-degree peeling adhesion above the above lower limit, the adhesion is more excellent.

關於本實施方式之黏著性樹脂片材,將厚度50μm之黏著性樹脂片材貼合於霧度值為0.1%之玻璃上並藉由霧度計測定之霧度值較佳為2.0%以下,更佳為1.8%以下,進而較佳為1.6%以下,尤佳為1.3%以下,最佳為1.0%以下,該厚度50μm之黏著性樹脂片材係將上述黏著性樹脂組合物塗敷於厚度38μm之經剝離處理之聚對苯二甲酸乙二酯膜上,於135℃下乾燥3分鐘使其硬化後,於23℃、50%RH環境下保管7天,自上述經剝離處理之聚對苯二甲酸乙二酯膜剝離所得。藉由使霧度值為上述上限值以下,透明性更優異。另一方面,上述黏著性樹脂片材之霧度值之下限值並無特別限定,越接近0.0%越好,例如可設為0.0%,亦可設為0.05%。 Regarding the adhesive resin sheet of the present embodiment, the adhesive resin sheet having a thickness of 50 μm is attached to a glass having a haze value of 0.1% and the haze value measured by a haze meter is preferably 2.0% or less, more preferably 1.8% or less, further preferably 1.6% or less, particularly preferably 1.3% or less, and most preferably 1.0% or less. The adhesive resin sheet having a thickness of 50 μm is obtained by applying the above-mentioned adhesive resin composition on a polyethylene terephthalate film having a thickness of 38 μm and subjected to a peeling treatment, drying at 135°C for 3 minutes to harden it, and then storing it at 23°C and 50% RH for 7 days, and peeling it from the above-mentioned polyethylene terephthalate film having been subjected to a peeling treatment. By making the haze value below the above upper limit, the transparency is better. On the other hand, the lower limit of the haze value of the above adhesive resin sheet is not particularly limited, and the closer to 0.0%, the better. For example, it can be set to 0.0% or 0.05%.

《積層膜》 《Accumulative membrane》

本實施方式之積層膜係膜基材積層於上述黏著性樹脂片材之至少一個面而成。 The laminated film of this embodiment is formed by laminating a film substrate on at least one surface of the above-mentioned adhesive resin sheet.

本實施方式之積層膜適合用於光學構件,尤其是適合用於光學用途中之貼附於金屬薄膜或金屬電極之用途。作為金屬薄膜,可例舉包含金屬、金屬氧化物或其等之混合物之薄膜,並無特別限定,例如可例舉ITO(氧化銦錫)、ZnO、SnO、CTO(氧化鎘錫)之薄膜。金屬薄膜之厚度並無特別限定,為10~200nm左右。通常ITO等之金屬薄膜例如設置於聚對苯二甲酸乙二酯膜(PET膜)等透明塑膠膜基材上,用作透明導電性膜。於將本實施方式之積層膜貼附於金屬薄膜時,較佳為將黏著性樹脂片材側之表面貼附於金屬薄膜。 The laminated film of this embodiment is suitable for use in optical components, and is particularly suitable for use in optical applications where it is attached to a metal film or metal electrode. As the metal film, there are examples of films containing metals, metal oxides, or mixtures thereof, without particular limitation, such as ITO (indium tin oxide), ZnO, SnO, and CTO (cadmium tin oxide) films. The thickness of the metal film is not particularly limited, and is about 10 to 200 nm. Usually, metal films such as ITO are disposed on transparent plastic film substrates such as polyethylene terephthalate films (PET films) and used as transparent conductive films. When attaching the laminated film of this embodiment to the metal film, it is preferred to attach the surface of the adhesive resin sheet side to the metal film.

又,作為上述金屬電極,為包含金屬、金屬氧化物或其等之混合物之電極即可,並無特別限定,例如可例舉ITO、銀、銅、CNT(奈米碳管)之電極。 Furthermore, the metal electrode mentioned above may be an electrode containing a metal, a metal oxide or a mixture thereof, and is not particularly limited. Examples thereof include electrodes of ITO, silver, copper, and CNT (carbon nanotube).

作為本實施方式之積層膜之具體用途之一例,可例舉觸控面板。觸控面板用黏著片材例如用於在靜電電容方式之觸控面板之製造中,將設置有ITO等之金屬薄膜之透明導電膜與聚甲基丙烯酸甲酯樹脂(PMMA)板、硬塗膜、玻璃鏡片等貼合。上述觸控面板並無特別限定,例如可用於行動電話、平板電腦、攜帶型資訊終端等。 As an example of a specific use of the multilayer film of this embodiment, a touch panel can be cited. The adhesive sheet for touch panels is used, for example, in the manufacture of electrostatic capacitive touch panels to bond a transparent conductive film provided with a metal film such as ITO to a polymethyl methacrylate resin (PMMA) plate, a hard coating film, a glass lens, etc. The above-mentioned touch panel is not particularly limited, and can be used, for example, in mobile phones, tablet computers, portable information terminals, etc.

又,作為本實施方式之積層膜之膜基材,可使用光學構件。於該情形時,可藉由將上述黏著性樹脂組合物直接塗佈於光學構件,並乾燥去除聚合溶劑等,而獲得黏著性樹脂片材形成於光學構件之黏著型光學構件。或者,可將經剝離處理之形成於隔片之黏著性樹脂片材適當轉印於光學構件,而獲得黏著型光學構件。 Furthermore, an optical component can be used as a film substrate of the laminated film of this embodiment. In this case, the above-mentioned adhesive resin composition can be directly applied to the optical component and dried to remove the polymerization solvent, etc., to obtain an adhesive optical component in which the adhesive resin sheet is formed on the optical component. Alternatively, the adhesive resin sheet formed on the spacer after the peeling treatment can be appropriately transferred to the optical component to obtain an adhesive optical component.

再者,上述黏著型光學構件之製作時所使用之經剝離處理之片材可直接用作黏著型光學構件之隔片,可於步驟方面簡化。 Furthermore, the peeled sheet used in the production of the above-mentioned adhesive optical component can be directly used as a spacer for the adhesive optical component, which can simplify the steps.

又,於上述黏著型光學構件中,黏著劑層之形成時,可於光學構件之表面形成固定層,或實施電暈處理、電漿處理等各種易接著處理後,形成黏著劑層。又,黏著劑層之表面可進行易接著處理。 Furthermore, in the above-mentioned adhesive optical component, when forming the adhesive layer, a fixed layer can be formed on the surface of the optical component, or the adhesive layer can be formed after various easy-to-bond treatments such as corona treatment and plasma treatment. Furthermore, the surface of the adhesive layer can be subjected to easy-to-bond treatment.

上述黏著型光學構件可藉由使用透明導電性膜作為光學構件,而用作帶黏著劑層之透明導電性膜。透明導電性膜於透明塑膠膜基材之一面,具有作為透明導電性薄膜之上述ITO等之金屬薄膜。於透明塑膠膜基材之另一面,具有本實施方式之積層膜。於透明塑膠膜基材上,可經由底塗層設置透明導電性薄膜。再者,底塗層可設置複數層。於透明塑膠膜基材與黏著性樹脂片材之間可設置低聚物移動防止層。 The above-mentioned adhesive optical component can be used as a transparent conductive film with an adhesive layer by using a transparent conductive film as an optical component. The transparent conductive film has a metal film such as the above-mentioned ITO as a transparent conductive film on one side of a transparent plastic film substrate. On the other side of the transparent plastic film substrate, there is a laminated film of this embodiment. On the transparent plastic film substrate, a transparent conductive film can be provided via a primer layer. Furthermore, the primer layer can be provided in multiple layers. An oligomer migration prevention layer can be provided between the transparent plastic film substrate and the adhesive resin sheet.

作為上述透明塑膠膜基材,並無特別限制,可使用具有透明性之各種塑膠膜。該塑膠膜可由1層膜形成。例如,作為其材料,可例舉聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系樹脂、乙酸酯系樹脂、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、(甲基)丙烯酸系樹脂、聚氯乙烯系樹脂、聚偏二氯乙烯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、聚芳酯系樹脂、聚苯硫醚系樹脂、三乙醯纖維素系樹脂等。該等之中,尤佳為聚酯系樹脂、聚醯亞胺系樹脂及聚醚碸系樹脂。上述膜基材之厚度較佳為15~200μm。 As the transparent plastic film substrate, there is no particular limitation, and various plastic films with transparency can be used. The plastic film can be formed by a single layer of film. For example, as its material, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, triacetyl cellulose resins, etc. can be cited. Among them, polyester resins, polyimide resins and polyether sulfone resins are particularly preferred. The thickness of the above-mentioned film substrate is preferably 15~200μm.

上述膜基材其表面可預先實施濺鍍、電暈放電、火焰、紫外線照射、電子束照射、化學處理、氧化等蝕刻處理或底塗處理,而提昇其上設置之透明導電性薄膜或底塗層與上述膜基材之密接性。又,於設置透明導電性薄膜或底塗層前,可視需要藉由溶劑清洗或超音波清洗等進行除塵、潔淨化。 The surface of the above-mentioned film substrate may be subjected to etching treatment or primer treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical treatment, oxidation, etc. in advance to improve the adhesion between the transparent conductive film or primer layer disposed thereon and the above-mentioned film substrate. In addition, before the transparent conductive film or primer layer is disposed, dust removal and cleaning may be performed by solvent cleaning or ultrasonic cleaning as needed.

上述透明導電性薄膜之構成材料、厚度並無特別限定,如上述金屬薄膜中所例示。底塗層可由無機物、有機物或無機物與有機物之混合物形成。例如,作為無機物,可例舉NaF(1.3)、Na3AlF6(1.35)、LiF(1.36)、MgF2(1.38)、CaF2(1.4)、BaF2(1.3)、SiO2(1.46)、LaF3(1.55)、CeF3(1.63)、Al2O3(1.63)等無機物[上述各材料之()內之數值係光之折射率]。該等之中,較佳為SiO2、MgF2、Al2O3等,尤佳為SiO2。除上述以外,可使用相對於氧化銦包含氧化鈰10~40重量份左右、氧化錫0~20重量份左右之複合氧化物。 The constituent material and thickness of the transparent conductive film are not particularly limited, as exemplified in the metal film. The base coating layer may be formed of an inorganic substance, an organic substance, or a mixture of an inorganic substance and an organic substance. For example, as inorganic substances, there may be cited NaF (1.3), Na 3 AlF 6 (1.35), LiF (1.36), MgF 2 (1.38), CaF 2 (1.4), BaF 2 (1.3), SiO 2 (1.46), LaF 3 (1.55), CeF 3 (1.63), Al 2 O 3 (1.63), etc. [The values in parentheses of the above materials are the refractive index of light]. Among them, SiO 2 , MgF 2 , Al 2 O 3 , etc. are preferred, and SiO 2 is particularly preferred. In addition to the above, a composite oxide containing about 10 to 40 parts by weight of calcium oxide and about 0 to 20 parts by weight of tin oxide relative to indium oxide can be used.

又,作為有機物,可例舉丙烯酸樹脂、聚胺酯樹脂、三聚氰胺樹脂、醇酸樹脂、矽氧烷系聚合物、有機矽烷縮合物等。該等有機物至少使用1種。作為有機物,尤其是使用包含三聚氰胺樹脂、醇酸樹脂及有機矽烷縮合物之混合物之熱硬化型樹脂較理想。 In addition, as organic materials, acrylic resins, polyurethane resins, melamine resins, alkyd resins, silicone polymers, organic silane condensates, etc. can be cited. At least one of these organic materials is used. As the organic material, it is particularly desirable to use a thermosetting resin that is a mixture of melamine resins, alkyd resins, and organic silane condensates.

底塗層之厚度並無特別限制,基於光學設計、防止低聚物自上述膜基材產生之效果之方面而言,通常為1~300nm左右,較佳為5~300nm。 There is no particular restriction on the thickness of the base coating layer. Based on the optical design and the effect of preventing oligomers from being generated from the above-mentioned film substrate, it is usually around 1~300nm, preferably 5~300nm.

上述帶黏著劑層之透明導電性膜可用於觸控面板或液晶顯示器、有機EL(electroluminescence,電致發光)顯示器等各種裝置之形成等。尤其是適合用作觸控面板用電極板。觸控面板適合用於各種檢測方式(例如電阻膜方式、靜電電容方式等)。 The transparent conductive film with adhesive layer can be used in the formation of various devices such as touch panels, liquid crystal displays, organic EL (electroluminescence) displays, etc. It is particularly suitable for use as an electrode plate for touch panels. The touch panel is suitable for various detection methods (such as resistance film method, electrostatic capacitance method, etc.).

關於靜電電容方式之觸控面板,通常具備具有規定之圖案形狀之透明導電性薄膜之透明導電性膜形成於顯示器顯示部之整個面。上述帶黏著劑層之透明導電性膜以黏著劑層與圖案化之透明導電性薄膜面對面之方式適當積層。 Regarding the electrostatic capacitive touch panel, a transparent conductive film having a prescribed pattern shape is usually formed on the entire surface of the display portion of the display. The transparent conductive film with the adhesive layer is appropriately laminated in a manner that the adhesive layer and the patterned transparent conductive film face to face.

又,上述黏著型光學構件可藉由使用圖像顯示裝置用之光學膜作為光學構件,而用作帶黏著劑層之光學膜。 Furthermore, the above-mentioned adhesive optical component can be used as an optical film with an adhesive layer by using an optical film for an image display device as an optical component.

作為光學膜,可使用液晶顯示裝置、有機EL顯示裝置等圖像顯示裝置之形成中所使用者,其種類並無特別限制。例如,作為光學膜,可例舉偏光板。偏光板一般使用於偏光元件之一個面或兩個面具有透明保護膜者。 As an optical film, it can be used in the formation of image display devices such as liquid crystal display devices and organic EL display devices, and its type is not particularly limited. For example, as an optical film, a polarizing plate can be cited. Polarizing plates are generally used in polarizing elements with a transparent protective film on one or both sides.

[實施例] [Implementation example]

以下基於實施例及比較例對本實施方式更詳細地進行說明,但本實施方式完全不受以下實施例限定。 The present embodiment is described in more detail below based on embodiments and comparative examples, but the present embodiment is not limited to the following embodiments.

<試驗項目> <Test items>

對於實施例及比較例中製造之聚異氰酸酯組合物,按照以下所示之方法,進行各物性之測定及各評價。 For the polyisocyanate compositions produced in the examples and comparative examples, various physical properties were measured and evaluated according to the methods shown below.

[物性1] [Physical properties 1]

(異氰酸基含有率) (Isocyanate group content)

首先,準確稱量2g以上3g以下之測定試樣(W g)置於燒瓶中。其次,添加甲苯20mL,使測定試樣溶解。其次,添加2當量濃度之二正丁胺之甲苯溶液20mL,混合後,於室溫下放置15分鐘。其次,添加異丙醇70mL並混合。其次,將該液藉由1當量濃度之鹽酸溶液(因子F)滴定於指示劑。將所得之滴定值設為V2 mL。其次,於無聚異氰酸酯試樣之情形時,將所得之滴定值設為V1 ml。其次,由下述式算出聚異氰酸酯組合物之異氰酸基含有率(NCO%)(質量%)。再者,NCO%採用於不包含溶劑之狀態下算出之值。 First, accurately weigh a test sample (W g) of more than 2 g but less than 3 g and place it in a flask. Next, add 20 mL of toluene to dissolve the test sample. Next, add 20 mL of a 2-N concentration di-n-butylamine toluene solution, mix, and place at room temperature for 15 minutes. Next, add 70 mL of isopropanol and mix. Next, titrate the solution with a 1-N concentration hydrochloric acid solution (factor F) into the indicator. Set the obtained titration value as V2 mL. Next, in the absence of a polyisocyanate sample, set the obtained titration value as V1 ml. Next, calculate the isocyanate group content (NCO%) (mass %) of the polyisocyanate composition by the following formula. In addition, NCO% is the value calculated without the solvent.

異氰酸基含有率(質量%)=(V1-V2)×F×42/(W×1000)×100 Isocyanate group content (mass %) = (V1-V2) × F × 42/(W × 1000) × 100

[物性2] [Physical properties 2]

(數量平均分子量及重量平均分子量) (Number average molecular weight and weight average molecular weight)

數量平均分子量及重量平均分子量係藉由使用下述裝置之凝膠滲透層析法(GPC)測定所得之基於聚苯乙烯之數量平均分子量及重量平均分子量。 The number average molecular weight and weight average molecular weight are based on polystyrene and are measured by gel permeation chromatography (GPC) using the following apparatus.

(測定條件) (Measurement conditions)

裝置:Tosoh(股)製造、HLC-802A Device: Tosoh Co., Ltd., HLC-802A

管柱:Tosoh(股)製造、G1000HXL×1根G2000HXL×1根G3000HXL×1根 Column: Made by Tosoh Co., Ltd., G1000HXL × 1 piece, G2000HXL × 1 piece, G3000HXL × 1 piece

載體:四氫呋喃 Carrier: Tetrahydrofuran

檢測方法:示差折射計 Testing method: differential refractometer

[物性3] [Physical properties 3]

(平均異氰酸基官能基數) (Average number of isocyanate functional groups)

聚異氰酸酯組合物之平均異氰酸基官能基數(平均NCO數)係藉由下述式求出。再者,式中,「Mn」意指數量平均分子量,使用上述「物性2」中測定之值。「NCO%」使用上述「物性1」中算出之值。 The average isocyanate functional group number (average NCO number) of the polyisocyanate composition is calculated by the following formula. In the formula, "Mn" means the number average molecular weight, and the value measured in the above "Physical Property 2" is used. "NCO%" uses the value calculated in the above "Physical Property 1".

平均異氰酸基官能基數=(Mn×NCO%×0.01)/42 Average number of isocyanate functional groups = (Mn×NCO%×0.01)/42

[物性4] [Physical properties 4]

(玻璃轉移溫度Tg) (Glass transition temperature Tg)

樹脂組合物製作用多元醇及含有交聯性官能基之聚合物之玻璃轉移溫度係使用以下值,該值係對於使丙烯酸多元醇溶液或含有交聯性官能基之聚合物溶液中之有機溶劑及水分於減壓下飛散後進行真空乾燥所得者,使用示差掃描熱量(DSC)測定裝置於升溫速度5℃/分鐘之條件下進行測定所得。 The glass transition temperature of the polyol and the polymer containing cross-linking functional groups used in the preparation of the resin composition is the following value, which is obtained by dispersing the organic solvent and water in the acrylic polyol solution or the polymer solution containing cross-linking functional groups under reduced pressure and then vacuum drying, and measuring it using a differential scanning calorimeter (DSC) measuring device at a heating rate of 5°C/min.

[由聚異氰酸酯組合物單獨構成之硬化膜1之製作] [Preparation of a hardened film 1 composed solely of a polyisocyanate composition]

將各聚異氰酸酯組合物使用塗敷器塗敷於剝離膜上,於23℃、65%濕度環境下保管168小時後,獲得膜厚為40μm之硬化膜。 Each polyisocyanate composition was applied to the release film using an applicator and stored at 23°C and 65% humidity for 168 hours to obtain a cured film with a thickness of 40μm.

[評價1] [Evaluation 1]

(硬化膜之柔軟性) (Softness of hardened film)

對於硬化膜,藉由柯尼希硬度計(BYK Gardner公司之Pendulum hardness tester)測定於23℃環境下之柯尼希硬度(次)。將柯尼希硬度為60次以下者評價為硬度較低、柔軟性良好。 For the hardened film, the Koenig hardness (times) in a 23°C environment is measured using a Koenig hardness tester (BYK Gardner's Pendulum hardness tester). Those with a Koenig hardness of 60 times or less are evaluated as having low hardness and good softness.

[硬化膜2之製作] [Production of hardened film 2]

以聚異氰酸酯組合物之異氰酸基相對於樹脂組合物製作用多元醇之羥基之莫耳比NCO/OH為1之方式,將各聚異氰酸酯組合物與樹脂組合物製作用多元醇加以混合,獲得樹脂組合物。將所得之各樹脂組合物藉由塗敷器塗敷於聚丙烯(PP)板上,於90℃下硬化30分鐘,於23℃、65%濕度環境下保管168小時,獲得膜厚為40μm之硬化膜2。 The polyisocyanate compositions and the resin composition-preparing polyols were mixed in such a manner that the molar ratio of the isocyanate group of the polyisocyanate composition to the hydroxyl group of the resin composition-preparing polyol (NCO/OH) was 1, thereby obtaining resin compositions. The obtained resin compositions were applied to a polypropylene (PP) plate by an applicator, cured at 90°C for 30 minutes, and stored at 23°C and 65% humidity for 168 hours to obtain a cured film 2 with a film thickness of 40μm.

[評價2] [Evaluation 2]

(伸長率為140%時之應力、伸長率、及拉伸斷裂應力) (Stress, elongation, and tensile fracture stress at 140% elongation)

對於所得之硬化膜2,將寬度10mm、長度100mm之試驗片以夾具距離為20mm之方式置於拉伸試驗機,以速度20mm/分鐘進行拉伸試驗,對伸長率為140%時之應力、伸長率、及拉伸斷裂應力進行測定。將伸長率為140%時之應力為25.0MPa以下者、伸長率為140%以上者、及拉伸斷裂應力為伸長率為140%時之應力之1.2倍以上者,分別評價為伸長率為140%時之應力、伸長率及拉伸斷裂應力相對於伸長率為140%時之應力之比良好。又,將伸長率較大、伸長率為140%時之應力較低且拉伸斷裂應力為上述伸長率為140%時之應力之1.2倍以上者,評價為耐彎曲性更好。 For the obtained cured film 2, a test piece with a width of 10 mm and a length of 100 mm was placed in a tensile testing machine with a clamp distance of 20 mm, and a tensile test was performed at a speed of 20 mm/min to measure the stress, elongation, and tensile fracture stress at an elongation of 140%. The stress at an elongation of 140% was 25.0 MPa or less, the elongation was 140% or more, and the tensile fracture stress was 1.2 times or more of the stress at an elongation of 140%, and the ratio of the stress at an elongation of 140%, the elongation, and the tensile fracture stress to the stress at an elongation of 140% was evaluated as good. In addition, the ones with larger elongation, lower stress at 140% elongation and tensile fracture stress of 1.2 times or more of the stress at 140% elongation are evaluated as having better bending resistance.

[黏著性樹脂組合物X之製作] [Preparation of adhesive resin composition X]

相對於含有交聯性官能基之聚合物(丙烯酸系聚合物)OH1之固形物成分100質量份,添加各聚異氰酸酯組合物1.0質量份(固形物成分量)及乙酸乙酯,製作固形物成分為25質量%之黏著性樹脂組合物X。 Relative to 100 parts by weight of the solid content of the polymer (acrylic polymer) OH1 containing a crosslinking functional group, 1.0 parts by weight (solid content) of each polyisocyanate composition and ethyl acetate were added to prepare an adhesive resin composition X with a solid content of 25% by weight.

[黏著性樹脂組合物Y之製作] [Preparation of adhesive resin composition Y]

相對於含有交聯性官能基之聚合物(丙烯酸系聚合物)OH2之固形物成分100質量份,添加各聚異氰酸酯組合物2.0質量份(固形物成分量)及乙酸乙酯,製作固形物成分為25質量%之黏著性樹脂組合物Y。 Relative to 100 parts by weight of the solid content of the polymer (acrylic polymer) OH2 containing a crosslinking functional group, 2.0 parts by weight (solid content) of each polyisocyanate composition and ethyl acetate were added to prepare an adhesive resin composition Y with a solid content of 25% by weight.

[黏著性樹脂片材之製作1] [Production of adhesive resin sheet 1]

(180度剝離黏著力測定用黏著性樹脂片材之製作) (Preparation of adhesive resin sheet for 180 degree peeling adhesion measurement)

以乾燥後之厚度為50μm之方式,將黏著性樹脂組合物X或黏著性樹脂組合物Y藉由塗敷器塗敷於厚度25μm之聚對苯二甲酸乙二酯(PET)膜上,於135℃下乾燥3分鐘。其後,於23℃、50%RH環境下保管7天,獲得180度剝離黏著力測定用黏著性樹脂片材。 Adhesive resin composition X or adhesive resin composition Y was applied to a 25 μm thick polyethylene terephthalate (PET) film by an applicator in such a way that the thickness after drying was 50 μm, and dried at 135°C for 3 minutes. Thereafter, the film was stored at 23°C and 50% RH for 7 days to obtain an adhesive resin sheet for 180-degree peel adhesion measurement.

[評價3] [Rating 3]

(黏著力) (Adhesion)

將具備上述「黏著性樹脂片材之製作1」中所得之厚度50μm、寬度20mm及長度100mm之黏著性樹脂片材之積層體,貼附於作為被黏著體之SUS304BA板上,使用2kg輥進行1次往復壓接,於23℃下固化30分鐘後,使用拉伸試驗機以速度300mm/分鐘於23℃下測定180度剝離黏著 力。將180度剝離黏著力為0.05N/20mm以上者評價為黏著力良好。 The laminated body of the adhesive resin sheet with a thickness of 50μm, a width of 20mm and a length of 100mm obtained in the above "Preparation of Adhesive Resin Sheet 1" was attached to the SUS304BA plate as the adherend, and a 2kg roller was used to perform a reciprocating press bonding once. After curing at 23℃ for 30 minutes, the 180-degree peeling adhesion was measured at a speed of 300mm/minute at 23℃ using a tensile tester. The 180-degree peeling adhesion of 0.05N/20mm or more was evaluated as good adhesion.

[黏著性樹脂片材之製作2] [Production of adhesive resin sheet 2]

(凝膠分率測定用黏著性樹脂片材之製作) (Preparation of adhesive resin sheets for gel fraction measurement)

以乾燥後之厚度為50μm之方式,將黏著性樹脂組合物X或黏著性樹脂組合物Y藉由塗敷器塗敷於厚度38μm之經剝離處理之PET膜上,於135℃下乾燥3分鐘。其後,於23℃、50%RH環境下保管7天,獲得凝膠分率測定用黏著性樹脂片材。 Adhesive resin composition X or adhesive resin composition Y was applied to a 38 μm thick PET film that had been peeled by an applicator in such a way that the thickness after drying was 50 μm, and dried at 135°C for 3 minutes. Thereafter, it was stored at 23°C and 50% RH for 7 days to obtain an adhesive resin sheet for gel fraction measurement.

[評價4] [Rating 4]

(硬化性) (hardening)

採用約0.1g以上0.2g以下之上述「黏著性樹脂片材之製作2」中所得之黏著性樹脂片材,用網狀片材包裹,浸漬於乙酸乙酯中1週後,於120℃下乾燥2小時。其次,使用下式算出凝膠分率(質量%)。將凝膠分率為20.0質量%以上者評價為硬化性良好。 Use about 0.1g to 0.2g of the adhesive resin sheet obtained in the above "Adhesive resin sheet preparation 2", wrap it with a mesh sheet, immerse it in ethyl acetate for 1 week, and dry it at 120℃ for 2 hours. Then, calculate the gel fraction (mass %) using the following formula. Those with a gel fraction of 20.0 mass % or more are evaluated as having good curability.

(凝膠分率)=(乾燥後之樣品質量)/(乙酸乙酯投入前之樣品質量)×100 (Gel fraction) = (sample mass after drying) / (sample mass before ethyl acetate addition) × 100

[黏著性樹脂片材之製作3] [Production of adhesive resin sheet 3]

(具備霧度值測定用黏著性樹脂片材之積層體之製作) (Preparation of a laminate with adhesive resin sheets for haze value measurement)

將黏著性樹脂組合物X或黏著性樹脂組合物Y塗敷於厚度38μm之經剝離處理之聚對苯二甲酸乙二酯膜上,於135℃下乾燥3分鐘使其硬化後,於23℃、50%RH環境下保管7天,自上述經剝離處理之聚對苯二甲酸 乙二酯膜剝離,獲得厚度50μm之黏著性樹脂片材,將該黏著性樹脂片材貼合於霧度值為0.1%之玻璃上,獲得具備霧度值測定用黏著性樹脂片材之積層體。 Adhesive resin composition X or adhesive resin composition Y was applied to a 38 μm thick polyethylene terephthalate film that had been subjected to peeling treatment, dried at 135°C for 3 minutes to harden, and then stored at 23°C and 50% RH for 7 days. The adhesive resin sheet with a thickness of 50 μm was obtained by peeling off the above-mentioned polyethylene terephthalate film that had been subjected to peeling treatment. The adhesive resin sheet was bonded to a glass with a haze value of 0.1% to obtain a laminate having an adhesive resin sheet for measuring haze value.

[評價5] [Rating 5]

(透明性) (Transparency)

對於將上述「聚異氰酸酯組合物之硬化膜之製作」中所得之硬化膜貼合於霧度值為0.1%之玻璃上所得之積層體及上述「黏著性樹脂片材之製作3」中所得之積層體,將各積層體之2個面中之玻璃之相反側之面(即塗佈有聚異氰酸酯組合物或黏著性樹脂組合物之面)配置於光源側,使用Suga Test Instruments製造之霧度計(HMG-2DP)測定霧度。將霧度值為3.0%以下者評價為透明性良好。 For the laminate obtained by laminating the cured film obtained in the above "Preparation of the Cured Film of the Polyisocyanate Composition" on a glass with a haze value of 0.1% and the laminate obtained in the above "Preparation of the Adhesive Resin Sheet 3", the surface on the opposite side of the glass (i.e. the surface coated with the polyisocyanate composition or the adhesive resin composition) of the two surfaces of each laminate was placed on the light source side, and the haze was measured using a haze meter (HMG-2DP) manufactured by Suga Test Instruments. The haze value of 3.0% or less was evaluated as having good transparency.

<樹脂組合物製作用多元醇之製造> <Manufacturing of polyols using resin compositions>

[合成例1-1] [Synthesis Example 1-1]

(樹脂組合物製作用多元醇之製造) (Manufacturing of polyols using resin compositions)

於具備攪拌裝置、溫度計、冷卻管、氮氣導入口之四口燒瓶中,添加乙酸丁酯:29質量份,一面通入氮氣,一面升溫至112℃。於到達112℃後,停止通入氮氣,歷時5小時滴加包含甲基丙烯酸2-羥基乙酯:22.3質量份、甲基丙烯酸甲酯:8.0質量份、丙烯酸丁酯:26.1質量份、苯乙烯:42.3質量份、丙烯酸:1.3質量份、及2,2'-偶氮二(異丁腈):2質量份之混合物。其次,於115℃下一面通入氮氣,一面攪拌3小時後,冷卻至60℃,投入乙酸丁酯溶液,獲得固形物成分量為60質量%之樹脂組合物製 作用多元醇之溶液。樹脂組合物製作用多元醇之玻璃轉移溫度Tg為29.5℃,相對於樹脂固形物成分之羥值為139mgKOH/g,重量平均分子量Mw為2.75×104In a four-necked flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen inlet, 29 parts by mass of butyl acetate was added, and the temperature was raised to 112°C while nitrogen was introduced. After reaching 112°C, the introduction of nitrogen was stopped, and a mixture containing 22.3 parts by mass of 2-hydroxyethyl methacrylate, 8.0 parts by mass of methyl methacrylate, 26.1 parts by mass of butyl acrylate, 42.3 parts by mass of styrene, 1.3 parts by mass of acrylic acid, and 2 parts by mass of 2,2'-azobis(isobutyronitrile) was added dropwise over 5 hours. Next, the mixture was stirred at 115°C while nitrogen was introduced for 3 hours, and then cooled to 60°C, and the butyl acetate solution was added to obtain a resin composition having a solid content of 60% by mass to prepare a polyol solution. The glass transition temperature Tg of the polyol prepared from the resin composition is 29.5°C, the hydroxyl value relative to the resin solid content is 139 mgKOH/g, and the weight average molecular weight Mw is 2.75×10 4 .

<含有交聯性官能基之聚合物之合成> <Synthesis of polymers containing cross-linking functional groups>

[合成例2-1] [Synthesis Example 2-1]

(含有交聯性官能基之聚合物(丙烯酸系聚合物)OH1之合成) (Synthesis of polymer OH1 containing cross-linking functional groups (acrylic polymer))

於具備攪拌機、溫度計、氮氣導入管及冷卻管之四口燒瓶中,投入丙烯酸正丁酯(BA)97質量份及丙烯酸4-羥基丁酯(4-HBA)3質量份,並投入作為溶劑之乙酸乙酯145質量份。其次,一面於氮氣氛圍下進行攪拌,一面投入作為聚合起始劑之2,2'-偶氮二異丁腈(AIBN)0.14質量份,於63℃下反應9小時。反應後,進行冷卻,獲得固形物成分濃度為42.1質量%之丙烯酸系聚合物OH1。去除丙烯酸系聚合物OH1之溶劑測得之玻璃轉移溫度為-54.0℃,重量平均分子量為8.2×105In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a cooling tube, 97 parts by mass of n-butyl acrylate (BA) and 3 parts by mass of 4-hydroxybutyl acrylate (4-HBA) were added, and 145 parts by mass of ethyl acetate as a solvent was added. Next, while stirring under a nitrogen atmosphere, 0.14 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and the reaction was carried out at 63°C for 9 hours. After the reaction, the reaction was cooled to obtain an acrylic polymer OH1 with a solid content concentration of 42.1% by mass. The glass transition temperature of the acrylic polymer OH1 measured by removing the solvent was -54.0°C, and the weight average molecular weight was 8.2×10 5 .

[合成例2-2] [Synthesis Example 2-2]

(含有交聯性官能基之聚合物(丙烯酸系聚合物)OH2之合成) (Synthesis of polymers containing cross-linking functional groups (acrylic polymers) OH2)

於具備攪拌機、溫度計、氮氣導入管及冷卻管之四口燒瓶中,投入丙烯酸2-乙基己酯(2EHA)97質量份及丙烯酸4-羥基丁酯(4-HBA)3質量份,並投入作為溶劑之乙酸乙酯145質量份。其次,一面於氮氣氛圍下進行攪拌,一面投入作為聚合起始劑之2,2'-偶氮二異丁腈(AIBN)0.14質量份,於63℃下反應9小時。反應後,進行冷卻,獲得固形物成分濃度為42.2質量%之丙烯酸系聚合物OH2。去除丙烯酸系聚合物OH2之溶劑測得 之玻璃轉移溫度為-69.0℃,重量平均分子量為8.7×105In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a cooling tube, 97 parts by mass of 2-ethylhexyl acrylate (2EHA) and 3 parts by mass of 4-hydroxybutyl acrylate (4-HBA) were added, and 145 parts by mass of ethyl acetate as a solvent was added. Next, while stirring under a nitrogen atmosphere, 0.14 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the reaction was carried out at 63°C for 9 hours. After the reaction, the reaction was cooled to obtain an acrylic polymer OH2 with a solid content concentration of 42.2% by mass. The glass transition temperature of the acrylic polymer OH2 measured by removing the solvent was -69.0°C, and the weight average molecular weight was 8.7×10 5 .

<聚異氰酸酯組合物之製造> <Manufacturing of polyisocyanate compositions>

[實施例1] [Implementation Example 1]

(聚異氰酸酯組合物PA-a1之製造) (Manufacturing of polyisocyanate composition PA-a1)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、及二官能聚己內酯二醇(以下有時稱為「聚酯多元醇A1」)(Daicel公司製造,商品名「PLACCEL 220CPT」,數量平均分子量2000,羥值56.6mgKOH/g,酸值0.02mgKOH/g):120質量份(HDI之異氰酸基相對於聚酯多元醇A1之羥基之莫耳比為9.8之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為55.0質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物PA-a1。對於所得之聚異氰酸酯組合物PA-a1,藉由H-NMR(Hydrogen-Nuclear Magnetic Resonance,氫-核磁共振)及C-NMR(Carbon-Nuclear Magnetic Resonance,碳-核磁共振)進行分析,確認胺基甲酸酯鍵及脲基甲酸酯鍵之存在,該等鍵之中,胺基甲酸酯鍵之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸丁酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 100 parts by mass of HDI and 120 parts by mass of a difunctional polycaprolactone diol (hereinafter sometimes referred to as "polyester polyol A1") (manufactured by Daicel, trade name "PLACCEL 220CPT", number average molecular weight 2000, hydroxyl value 56.6 mgKOH/g, acid value 0.02 mgKOH/g) (the molar ratio of the isocyanate group of HDI to the hydroxyl group of the polyester polyol A1 is 9.8) were added under a nitrogen flow, and stirred, and the temperature in the reactor was maintained at 100°C. The reaction was stopped at the time point when the yield reached 55.0% by mass. After filtering the reaction solution, unreacted HDI was removed by thin film distillation to obtain polyisocyanate composition PA-a1. The obtained polyisocyanate composition PA-a1 was analyzed by H-NMR (Hydrogen-Nuclear Magnetic Resonance) and C-NMR (Carbon-Nuclear Magnetic Resonance) to confirm the presence of urethane bonds and allophanate bonds. Among these bonds, the molar ratio of urethane bonds was the highest. Then, butyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

再者,利用NMR(nuclear magnetic resonance,核磁共振)分析進行之結構之檢測係將各鍵之比率(莫耳%)相對於脲基甲酸酯基、脲二酮基、亞胺基

Figure 111129090-A0305-02-0047-9
Figure 111129090-A0305-02-0047-10
二酮基、異氰尿酸基、脲基、胺基甲酸酯基、及縮二脲基檢測到之合計莫耳量為1%以上者,計為該鍵存在。又,於以下實施例中亦採用相同方法,對鍵進行計數。 Furthermore, the structure was determined by NMR (nuclear magnetic resonance) analysis by measuring the ratio (molar %) of each bond relative to the allophanate group, uretdione group, imine group,
Figure 111129090-A0305-02-0047-9
two
Figure 111129090-A0305-02-0047-10
The total molar amount of diketone group, isocyanurate group, urea group, carbamate group, and biuret group detected is 1% or more, and the bond is counted. In addition, the same method is also used in the following examples to count the bonds.

[實施例2] [Example 2]

(聚異氰酸酯組合物PA-a2之製造) (Manufacturing of polyisocyanate composition PA-a2)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、及聚酯多元醇A1:135質量份(HDI之異氰酸基相對於聚酯多元醇A1之羥基之莫耳比為8.7之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為58.0質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物PA-a2。對於所得之聚異氰酸酯組合物PA-a2,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基及脲基甲酸酯基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸丁酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring wing, and a reflux cooling tube, 100 parts by mass of HDI and 135 parts by mass of polyester polyol A1 (the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 is 8.7) are added under a nitrogen flow and stirred, and the temperature in the reactor is maintained at 100°C. The reaction is stopped at the time point when the yield is 58.0% by mass. After filtering the reaction solution, unreacted HDI is removed by a thin film distillation device to obtain a polyisocyanate composition PA-a2. The obtained polyisocyanate composition PA-a2 is analyzed by H-NMR and C-NMR to confirm the presence of carbamate groups and allophanate groups. Among these groups, the molar ratio of carbamate groups is the largest. Then, butyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[實施例3] [Implementation Example 3]

(聚異氰酸酯組合物PA-a3之製造) (Manufacturing of polyisocyanate composition PA-a3)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、1,3-丁二醇:0.5質量份、及聚酯多元醇A1:125質量份(HDI之異氰酸基相對於聚酯多元醇A1之羥基之莫耳比為9.4之量)並進行攪拌,將反應器內溫度於160℃下保持20分鐘後,降至100℃並保持。於產率為56.0質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物PA-a3。對於所得之聚異氰酸酯組合物PA-a3,藉由H-NMR及C-NMR進行分析,確認 胺基甲酸酯基、脲基甲酸酯基、脲二酮基、及脲基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸丁酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring wing, and a reflux cooling tube, 100 parts by mass of HDI, 0.5 parts by mass of 1,3-butanediol, and 125 parts by mass of polyester polyol A1 (the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 is 9.4) were added under a nitrogen flow and stirred. The temperature in the reactor was maintained at 160°C for 20 minutes, then reduced to 100°C and maintained. The reaction was stopped at a yield of 56.0% by mass. After filtering the reaction solution, unreacted HDI was removed by a thin film distillation device to obtain a polyisocyanate composition PA-a3. The obtained polyisocyanate composition PA-a3 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate group, allophanate group, uretdione group, and urea group. Among these groups, the molar ratio of carbamate group was the largest. Then, butyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[實施例4] [Implementation Example 4]

(聚異氰酸酯組合物PA-a4之製造) (Manufacturing of polyisocyanate composition PA-a4)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、及二官能聚己內酯二醇(以下有時稱為「聚酯多元醇A2」)(Daicel公司製造,商品名「PLACCEL 230」,數量平均分子量3000,羥值37.6mgKOH/g,酸值0.07mgKOH/g):150質量份(HDI之異氰酸基相對於聚酯多元醇A2之羥基之莫耳比為11.8之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為60.5質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物PA-a4。對於所得之聚異氰酸酯組合物PA-a4,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基及脲基甲酸酯基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸丁酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為固體。 In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 100 parts by mass of HDI and 150 parts by mass of a difunctional polycaprolactone diol (hereinafter sometimes referred to as "polyester polyol A2") (manufactured by Daicel, trade name "PLACCEL 230", number average molecular weight 3000, hydroxyl value 37.6 mgKOH/g, acid value 0.07 mgKOH/g) (the molar ratio of the isocyanate group of HDI to the hydroxyl group of the polyester polyol A2 is 11.8) were added under a nitrogen flow, and stirred, and the temperature in the reactor was maintained at 100°C. The reaction was stopped at the time point when the yield reached 60.5% by mass. After filtering the reaction solution, unreacted HDI was removed by thin film distillation to obtain polyisocyanate composition PA-a4. The obtained polyisocyanate composition PA-a4 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate groups and allophanate groups. Among these groups, the molar ratio of carbamate groups was the highest. Then, butyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was solid at 23°C.

[實施例5] [Implementation Example 5]

(聚異氰酸酯組合物PA-a5之製造) (Manufacturing of polyisocyanate composition PA-a5)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流 下添加HDI:100質量份、及二官能聚己內酯二醇(以下有時稱為「聚酯多元醇A3」)(Daicel公司製造,商品名「PLACCEL 240」,數量平均分子量4000,羥值28.5mgKOH/g,酸值0.07mgKOH/g):200質量份(HDI之異氰酸基相對於聚酯多元醇A3之羥基之莫耳比為11.7之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為67.0質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物PA-a5。對於所得之聚異氰酸酯組合物PA-a5,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基及脲基甲酸酯基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸丁酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為固體。 In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 100 parts by mass of HDI and 200 parts by mass of difunctional polycaprolactone diol (hereinafter sometimes referred to as "polyester polyol A3") (manufactured by Daicel, trade name "PLACCEL 240", number average molecular weight 4000, hydroxyl value 28.5 mgKOH/g, acid value 0.07 mgKOH/g) (the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A3 is 11.7) were added under nitrogen flow and stirred, and the temperature in the reactor was maintained at 100°C. The reaction was stopped at the time point when the yield reached 67.0% by mass. After filtering the reaction solution, unreacted HDI was removed by thin film distillation to obtain polyisocyanate composition PA-a5. The obtained polyisocyanate composition PA-a5 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate groups and allophanate groups. Among these groups, the molar ratio of carbamate groups was the highest. Then, butyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was solid at 23°C.

[實施例6] [Implementation Example 6]

(聚異氰酸酯組合物PA-a6之製造) (Manufacturing of polyisocyanate composition PA-a6)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、2-乙基己醇:0.8質量份、及聚酯多元醇A1:125質量份(HDI之異氰酸基相對於聚酯多元醇A1之羥基之莫耳比為9.4之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為56.0質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物PA-a6。對於所得之聚異氰酸酯組合物PA-a6,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基及脲基甲酸酯基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸丁酯,稀釋成固形物成分為70質量%,該狀態 之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 100 parts by mass of HDI, 0.8 parts by mass of 2-ethylhexanol, and 125 parts by mass of polyester polyol A1 (the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 is 9.4) were added under a nitrogen flow and stirred, and the temperature in the reactor was maintained at 100°C. The reaction was stopped at a time point when the yield was 56.0% by mass. After filtering the reaction solution, unreacted HDI was removed by a thin film distillation device to obtain a polyisocyanate composition PA-a6. The obtained polyisocyanate composition PA-a6 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate groups and allophanate groups. Among these groups, the molar ratio of carbamate groups was the largest. Then, butyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[實施例7] [Implementation Example 7]

(聚異氰酸酯組合物PA-a7之製造) (Manufacturing of polyisocyanate composition PA-a7)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、1,3-丁二醇:0.5質量份、及聚酯多元醇A1:118質量份(HDI之異氰酸基相對於聚酯多元醇A1之羥基之莫耳比為10.0之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為54.7質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物之中間物。於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下相對於所得之聚異氰酸酯組合物之中間物100質量份添加聚酯多元醇A1:3質量份,於100℃下保持2小時,獲得聚異氰酸酯組合物PA-a7。對於所得之聚異氰酸酯組合物PA-a7,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基、脲基甲酸酯基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸丁酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 100 parts by mass of HDI, 0.5 parts by mass of 1,3-butanediol, and 118 parts by mass of polyester polyol A1 (the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 is 10.0) were added under a nitrogen flow and stirred, and the temperature in the reactor was maintained at 100°C. The reaction was stopped at a time point when the yield was 54.7% by mass. After filtering the reaction solution, the unreacted HDI was removed by a thin film distillation device to obtain an intermediate of a polyisocyanate composition. In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 1:3 parts by mass of polyester polyol A was added to 100 parts by mass of the intermediate of the obtained polyisocyanate composition under a nitrogen flow, and the mixture was kept at 100°C for 2 hours to obtain a polyisocyanate composition PA-a7. The obtained polyisocyanate composition PA-a7 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate groups and allophanate groups. Among these groups, the molar ratio of carbamate groups was the largest. Subsequently, butyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[實施例8] [Implementation Example 8]

(聚異氰酸酯組合物PA-a8之製造) (Manufacturing of polyisocyanate composition PA-a8)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、及三官能聚己內酯多元醇(以下有時稱為「聚酯多元醇B1」)(Daicel公司製造,商品名「PLACCEL 308」,數量平均分子 量850,羥值195.3mgKOH/g,酸值0.38mgKOH/g):37.5質量份(HDI之異氰酸基相對於聚酯多元醇B1之羥基之莫耳比為9.1之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為40.5質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物PA-a8。對於所得之聚異氰酸酯組合物PA-a8,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基及脲基甲酸酯基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸丁酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 100 parts by mass of HDI and 37.5 parts by mass of trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1") (manufactured by Daicel, trade name "PLACCEL 308", number average molecular weight 850, hydroxyl value 195.3 mgKOH/g, acid value 0.38 mgKOH/g) (the molar ratio of isocyanate group of HDI to hydroxyl group of polyester polyol B1 is 9.1) were added under nitrogen flow and stirred, and the temperature in the reactor was maintained at 100°C. The reaction was stopped at the time point when the yield reached 40.5% by mass. After filtering the reaction solution, unreacted HDI was removed by thin film distillation to obtain polyisocyanate composition PA-a8. The obtained polyisocyanate composition PA-a8 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate groups and allophanate groups. Among these groups, the molar ratio of carbamate groups was the highest. Then, butyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[實施例9~12] [Examples 9 to 12]

(聚異氰酸酯組合物PA-a9~PA-a12之製造) (Manufacturing of polyisocyanate compositions PA-a9~PA-a12)

除按照表2所示之配方以外,使用與實施例8相同之方法,製造各聚異氰酸酯組合物。對於所得之聚異氰酸酯組合物,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基及脲基甲酸酯基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸丁酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In addition to the formula shown in Table 2, each polyisocyanate composition was prepared using the same method as Example 8. The obtained polyisocyanate composition was analyzed by H-NMR and C-NMR to confirm the presence of carbamate groups and allophanate groups. Among these groups, the molar ratio of carbamate groups was the largest. Then, butyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[實施例13] [Implementation Example 13]

(聚異氰酸酯組合物PA-a13之製造) (Manufacturing of polyisocyanate composition PA-a13)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、1,3-丁二醇:1.0質量份、及聚酯多元醇A1: 115質量份(HDI之異氰酸基相對於聚酯多元醇A1之羥基之莫耳比為10.2之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為53.0質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物PA-a13。對於所得之聚異氰酸酯組合物PA-a13,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯鍵及脲基甲酸酯鍵之存在,該等鍵之中,胺基甲酸酯鍵之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸乙酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 100 parts by mass of HDI, 1.0 parts by mass of 1,3-butanediol, and 115 parts by mass of polyester polyol A1 (the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 is 10.2) were added under a nitrogen flow and stirred, and the temperature in the reactor was maintained at 100°C. The reaction was stopped at a yield of 53.0% by mass. After filtering the reaction solution, unreacted HDI was removed by a thin film distillation device to obtain a polyisocyanate composition PA-a13. The obtained polyisocyanate composition PA-a13 was analyzed by H-NMR and C-NMR to confirm the presence of urethane bonds and allophanate bonds. Among these bonds, the molar ratio of urethane bonds was the largest. Then, ethyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[實施例14] [Example 14]

(聚異氰酸酯組合物PA-a14之製造) (Manufacturing of polyisocyanate composition PA-a14)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、1,3-丁二醇:1.5質量份、及聚酯多元醇A1:112質量份(HDI之異氰酸基相對於聚酯多元醇A1之羥基之莫耳比為10.5之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為51.5質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物之中間物。於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下相對於所得之聚異氰酸酯組合物之中間物100質量份添加聚酯多元醇A1:3質量份,並以相對於樹脂分為90質量ppm添加酸式磷酸2-乙基己酯(城北化學工業公司製造,商品名「JP508T」),將反應器內溫度於95℃下保持120分鐘,獲得聚異氰酸酯成分PA-a14。對於所得之聚異氰酸酯組合物PA-a14,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基、脲基甲酸酯基之存在,該等基之 中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸乙酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 100 parts by mass of HDI, 1.5 parts by mass of 1,3-butanediol, and 112 parts by mass of polyester polyol A1 (the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 is 10.5) are added under a nitrogen flow and stirred, and the temperature in the reactor is maintained at 100°C. The reaction is stopped at a time point when the yield is 51.5% by mass. After filtering the reaction solution, unreacted HDI is removed by a thin film distillation device to obtain an intermediate of a polyisocyanate composition. In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 1:3 parts by mass of polyester polyol A was added to 100 parts by mass of the intermediate of the obtained polyisocyanate composition under a nitrogen flow, and 2-ethylhexyl acid phosphate (manufactured by Chengbei Chemical Industry Co., Ltd., trade name "JP508T") was added at 90 ppm by mass relative to the resin. The temperature in the reactor was maintained at 95°C for 120 minutes to obtain the polyisocyanate component PA-a14. The obtained polyisocyanate composition PA-a14 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate groups and allophanate groups. Among these groups, the molar ratio of carbamate groups was the largest. Thereafter, ethyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[實施例15] [Implementation Example 15]

(聚異氰酸酯組合物PA-a15之製造) (Manufacturing of polyisocyanate composition PA-a15)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、1,3-丁二醇:2.0質量份、及聚酯多元醇A1:130質量份(HDI之異氰酸基相對於聚酯多元醇A1之羥基之莫耳比為9.1之量)並進行攪拌,將反應器內溫度於160℃下保持20分鐘後,降至100℃並保持。於產率為56.3質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物之中間物。於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下相對於所得之聚異氰酸酯組合物之中間物100質量份添加聚酯多元醇A1:2質量份、甲基聚伸烷基二醇(重複單元n=15)0.2質量份並攪拌,並以相對於樹脂分為90質量ppm添加酸式磷酸2-乙基己酯(城北化學工業公司製造,商品名「JP508T」),將反應器內溫度於95℃下保持120分鐘,獲得聚異氰酸酯成分PA-a15。對於所得之聚異氰酸酯組合物PA-a15,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基、脲基甲酸酯基、脲二酮基、及脲基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸乙酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring wing, and a reflux cooling tube, 100 parts by mass of HDI, 2.0 parts by mass of 1,3-butanediol, and 130 parts by mass of polyester polyol A1 (the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 is 9.1) are added under a nitrogen flow and stirred. The temperature in the reactor is maintained at 160°C for 20 minutes, then reduced to 100°C and maintained. The reaction is stopped at a yield of 56.3% by mass. After filtering the reaction solution, unreacted HDI is removed by a thin film distillation device to obtain an intermediate of a polyisocyanate composition. In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 2 parts by mass of polyester polyol A1 and 0.2 parts by mass of methyl polyalkylene glycol (repeating unit n=15) were added to 100 parts by mass of the intermediate of the obtained polyisocyanate composition under a nitrogen flow and stirred. 2-ethylhexyl acid phosphate (manufactured by Chengbei Chemical Industry Co., Ltd., trade name "JP508T") was added at 90 ppm by mass relative to the resin. The temperature in the reactor was maintained at 95°C for 120 minutes to obtain polyisocyanate component PA-a15. The obtained polyisocyanate composition PA-a15 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate group, allophanate group, uretdione group, and urea group. Among these groups, the molar ratio of carbamate group was the highest. Then, ethyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[實施例16] [Implementation Example 16]

(聚異氰酸酯組合物PA-a16之製造) (Manufacturing of polyisocyanate composition PA-a16)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、1,3-丁二醇:2.5質量份、及聚酯多元醇A1:135質量份(HDI之異氰酸基相對於聚酯多元醇A1之羥基之莫耳比為8.7之量)並進行攪拌,將反應器內溫度於160℃下保持20分鐘後,降至100℃並保持。於產率為58.7質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物之中間物。於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下相對於所得之聚異氰酸酯組合物之中間物100質量份添加聚酯多元醇A1:3質量份,並以相對於樹脂分為90質量ppm添加酸式磷酸2-乙基己酯(城北化學工業公司製造,商品名「JP508T」),將反應器內溫度於95℃下保持120分鐘,獲得聚異氰酸酯成分PA-a16。對於所得之聚異氰酸酯組合物PA-a16,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基、脲基甲酸酯基、脲二酮基、及脲基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸乙酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring wing, and a reflux cooling tube, 100 parts by mass of HDI, 2.5 parts by mass of 1,3-butanediol, and 135 parts by mass of polyester polyol A1 (the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 is 8.7) are added under a nitrogen flow and stirred. The temperature in the reactor is maintained at 160°C for 20 minutes, then reduced to 100°C and maintained. The reaction is stopped at a yield of 58.7% by mass. After filtering the reaction solution, unreacted HDI is removed by a thin film distillation device to obtain an intermediate of a polyisocyanate composition. In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 1:3 parts by mass of polyester polyol A was added to 100 parts by mass of the intermediate of the obtained polyisocyanate composition under a nitrogen flow, and 2-ethylhexyl acid phosphate (manufactured by Chengbei Chemical Industry Co., Ltd., trade name "JP508T") was added at 90 ppm by mass relative to the resin, and the temperature in the reactor was maintained at 95°C for 120 minutes to obtain polyisocyanate component PA-a16. The obtained polyisocyanate composition PA-a16 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate group, allophanate group, uretdione group, and urea group. Among these groups, the molar ratio of carbamate group was the largest. Thereafter, ethyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[實施例17] [Example 17]

(聚異氰酸酯組合物PA-a17之製造) (Manufacturing of polyisocyanate composition PA-a17)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、及二官能聚己內酯二醇(以下有時稱為「聚酯多元醇A3」)(Daicel公司製造,商品名「PLACCEL 240」,數量平均分子量 4000,羥值28.5mgKOH/g,酸值0.07mgKOH/g):215質量份(HDI之異氰酸基相對於聚酯多元醇A3之羥基之莫耳比為10.9之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為69.0質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物PA-a17。對於所得之聚異氰酸酯組合物PA-a17,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基及脲基甲酸酯基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸乙酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為固體。 In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 100 parts by mass of HDI and 215 parts by mass of difunctional polycaprolactone diol (hereinafter sometimes referred to as "polyester polyol A3") (manufactured by Daicel, trade name "PLACCEL 240", number average molecular weight 4000, hydroxyl value 28.5 mgKOH/g, acid value 0.07 mgKOH/g) (the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A3 is 10.9) were added under a nitrogen flow and stirred, and the temperature in the reactor was maintained at 100°C. The reaction was stopped at the time point when the yield reached 69.0% by mass. After filtering the reaction solution, unreacted HDI was removed by thin film distillation to obtain polyisocyanate composition PA-a17. The obtained polyisocyanate composition PA-a17 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate groups and allophanate groups. Among these groups, the molar ratio of carbamate groups was the highest. Thereafter, ethyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was solid at 23°C.

[實施例18] [Implementation Example 18]

(聚異氰酸酯組合物PA-a18之製造) (Manufacturing of polyisocyanate composition PA-a18)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、及聚酯多元醇A1:115質量份(HDI之異氰酸基相對於聚酯多元醇A1之羥基之莫耳比為10.2之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為52.2質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物之中間物。於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下相對於所得之聚異氰酸酯組合物之中間物100質量份添加1,3-丁二醇:1.0質量份,將反應器內溫度於160℃下保持1小時,獲得聚異氰酸酯成分PA-a18。對於所得之聚異氰酸酯組合物PA-a18,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基、脲基甲酸酯基、脲二酮基、及脲基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚 異氰酸酯組合物中添加乙酸乙酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 100 parts by mass of HDI and 115 parts by mass of polyester polyol A1 (the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 is 10.2) were added under a nitrogen flow and stirred, and the temperature in the reactor was maintained at 100°C. The reaction was stopped at the time point when the yield was 52.2% by mass. After filtering the reaction solution, the unreacted HDI was removed by a thin film distillation device to obtain an intermediate of a polyisocyanate composition. In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 1.0 mass part of 1,3-butanediol was added to 100 mass parts of the intermediate of the obtained polyisocyanate composition under a nitrogen flow, and the temperature in the reactor was maintained at 160°C for 1 hour to obtain the polyisocyanate component PA-a18. The obtained polyisocyanate composition PA-a18 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate group, allophanate group, uretdione group, and urea group. Among these groups, the molar ratio of carbamate group was the largest. Thereafter, ethyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70 mass%. The polyisocyanate composition in this state was liquid at 23°C.

[實施例19] [Implementation Example 19]

(聚異氰酸酯組合物PA-a19之製造) (Manufacturing of polyisocyanate composition PA-a19)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、及三官能聚己內酯多元醇(以下有時稱為「聚酯多元醇B1」)(Daicel公司製造,商品名「PLACCEL 308」,數量平均分子量850,羥值195.3mgKOH/g,酸值0.38mgKOH/g):35.0質量份(HDI之異氰酸基相對於聚酯多元醇B1之羥基之莫耳比為9.8之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為40.7質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物之中間物。於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下相對於所得之聚異氰酸酯組合物之中間物100質量份添加聚酯多元醇B1 4.0質量份,並以相對於樹脂分為90質量ppm添加酸式磷酸2-乙基己酯(城北化學工業公司製造,商品名「JP508T」),將反應器內溫度於95℃下保持120分鐘,獲得聚異氰酸酯成分PA-a19。對於所得之聚異氰酸酯組合物PA-a19,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基及脲基甲酸酯基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸乙酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 100 parts by mass of HDI and 35.0 parts by mass of trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1") (manufactured by Daicel, trade name "PLACCEL 308", number average molecular weight 850, hydroxyl value 195.3 mgKOH/g, acid value 0.38 mgKOH/g) (the molar ratio of isocyanate group of HDI to hydroxyl group of polyester polyol B1 is 9.8) were added under nitrogen flow, and stirred, and the temperature in the reactor was maintained at 100°C. The reaction was stopped at the time point when the yield reached 40.7% by mass. After filtering the reaction solution, unreacted HDI was removed by thin film distillation to obtain an intermediate of a polyisocyanate composition. In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 4.0 parts by mass of polyester polyol B1 was added to 100 parts by mass of the intermediate of the obtained polyisocyanate composition under a nitrogen flow, and 2-ethylhexyl acid phosphate (manufactured by Johoku Chemical Industry Co., Ltd., trade name "JP508T") was added at 90 ppm by mass relative to the resin, and the temperature in the reactor was maintained at 95°C for 120 minutes to obtain a polyisocyanate component PA-a19. The obtained polyisocyanate composition PA-a19 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate groups and allophanate groups. Among these groups, the molar ratio of carbamate groups was the highest. Subsequently, ethyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[實施例20] [Example 20]

(聚異氰酸酯組合物PA-a20之製造) (Manufacturing of polyisocyanate composition PA-a20)

於安裝有溫度計、攪拌翼、回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI:100質量份、三官能聚己內酯多元醇(以下有時稱為「聚酯多元醇B1」)(Daicel公司製造,商品名「PLACCEL 308」,數量平均分子量850,羥值195.3mgKOH/g,酸值0.38mgKOH/g):36.0質量份、及三官能聚己內酯多元醇(以下有時稱為「聚酯多元醇B2」)(Daicel公司製造,商品名「PLACCEL 312」,數量平均分子量1250,羥值136.1mgKOH/g):4.0質量份(HDI之異氰酸基相對於聚酯多元醇B1與B2之羥基之莫耳比為8.8之量)並進行攪拌,將反應器內溫度保持於100℃。於產率為41.7質量%之時間點停止反應。對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI,獲得聚異氰酸酯組合物PA-a20。對於所得之聚異氰酸酯組合物PA-a20,藉由H-NMR及C-NMR進行分析,確認胺基甲酸酯基及脲基甲酸酯基之存在,該等基之中,胺基甲酸酯基之莫耳比率最多。其後,於所得之聚異氰酸酯組合物中添加乙酸乙酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux cooling tube, 100 parts by mass of HDI, 36.0 parts by mass of trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1") (manufactured by Daicel, trade name "PLACCEL 308", number average molecular weight 850, hydroxyl value 195.3 mgKOH/g, acid value 0.38 mgKOH/g), and 100 parts by mass of trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B2") (manufactured by Daicel, trade name "PLACCEL 312", number average molecular weight 1250, hydroxyl value 136.1 mgKOH/g): 4.0 parts by mass (the molar ratio of the isocyanate group of HDI to the hydroxyl group of the polyester polyols B1 and B2 is 8.8) and stirred, and the temperature in the reactor was maintained at 100°C. The reaction was stopped at the time point when the yield was 41.7% by mass. After filtering the reaction solution, the unreacted HDI was removed by a thin film distillation device to obtain a polyisocyanate composition PA-a20. The obtained polyisocyanate composition PA-a20 was analyzed by H-NMR and C-NMR to confirm the presence of carbamate groups and allophanate groups. Among these groups, the molar ratio of carbamate groups was the largest. Thereafter, ethyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[比較例1] [Comparison Example 1]

(聚異氰酸酯組合物PA-b1之製造) (Manufacturing of polyisocyanate composition PA-b1)

於安裝有溫度計、攪拌翼及回流冷卻管之四口燒瓶中,於氮氣氣流下添加HDI 100質量份及三羥甲基丙烷8.9質量份,一面攪拌一面將反應器內溫度保持於75℃ 5小時,進行胺基甲酸酯化反應。對反應液進行過濾後,使用薄膜蒸發罐去除未反應之HDI,獲得包含異氰尿酸酯型聚異氰酸酯之聚異氰酸酯組合物PA-b1。其後,於所得之聚異氰酸酯組合物中添加 乙酸丁酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In a four-necked flask equipped with a thermometer, a stirring blade and a reflux cooling tube, 100 parts by mass of HDI and 8.9 parts by mass of trihydroxymethylpropane were added under a nitrogen flow, and the temperature in the reactor was kept at 75°C for 5 hours while stirring to carry out the urethanization reaction. After filtering the reaction solution, the unreacted HDI was removed using a thin film evaporator to obtain a polyisocyanate composition PA-b1 containing an isocyanurate-type polyisocyanate. Subsequently, butyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[比較例2~3] [Comparison Example 2~3]

(聚異氰酸酯組合物PA-b2~PA-b3之製造) (Manufacturing of polyisocyanate compositions PA-b2~PA-b3)

除按照表3所示之配方以外,使用與實施例1相同之方法,獲得各聚異氰酸酯組合物。其後,於所得之聚異氰酸酯組合物中添加乙酸丁酯,稀釋成固形物成分為70質量%,該狀態之聚異氰酸酯組合物於23℃下為液體。 In addition to the formula shown in Table 3, the same method as Example 1 was used to obtain each polyisocyanate composition. Then, butyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass. The polyisocyanate composition in this state was liquid at 23°C.

[比較例4] [Comparison Example 4]

(聚異氰酸酯組合物PA-b4之製造) (Manufacturing of polyisocyanate composition PA-b4)

對安裝有攪拌器、溫度計、冷卻管之四口燒瓶之內部進行氮氣置換,添加HDI 1000g,於60℃下一面攪拌,一面同時添加作為觸媒之四甲基銨辛酸鹽0.09g、及異丁醇1.3g。4.5小時後,藉由反應液之折射率測定確認設定之反應終點,添加磷酸0.2g,停止反應。其後,對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI單體,藉此獲得聚異氰酸酯。所得之聚異氰酸酯之異氰酸基含有率為23.1質量%,異氰酸基平均官能基數為3.4。對於所得之聚異氰酸酯組合物PA-b4,藉由H-NMR及C-NMR進行分析,確認異氰尿酸基之存在,該等基之中,異氰尿酸基之莫耳比率最多。 The interior of a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube was replaced with nitrogen, and 1000 g of HDI was added. While stirring at 60°C, 0.09 g of tetramethylammonium octanoate and 1.3 g of isobutyl alcohol were added as catalysts. After 4.5 hours, the reaction endpoint was confirmed by measuring the refractive index of the reaction solution, and 0.2 g of phosphoric acid was added to stop the reaction. Afterwards, the reaction solution was filtered, and the unreacted HDI monomer was removed by a thin film distillation device to obtain polyisocyanate. The isocyanate content of the obtained polyisocyanate was 23.1% by mass, and the average functional group number of the isocyanate group was 3.4. The obtained polyisocyanate composition PA-b4 was analyzed by H-NMR and C-NMR to confirm the presence of isocyanuric acid groups. Among these groups, the molar ratio of isocyanuric acid groups is the highest.

[比較例5] [Comparison Example 5]

(聚異氰酸酯組合物PA-b5之製造) (Manufacturing of polyisocyanate composition PA-b5)

對安裝有攪拌器、溫度計、冷卻管之四口燒瓶之內部進行氮氣置換,將HDI 1000g、水7.2g、乙二醇單甲醚乙酸酯600g於常溫下混合,於140℃下於常壓下反應120分鐘。其後於160℃下反應1小時。未見沈澱物或渾濁。其後,對反應液進行過濾後,藉由薄膜蒸餾裝置去除未反應之HDI單體及溶劑,藉此獲得聚異氰酸酯。所得之聚異氰酸酯之異氰酸基含有率為23.4質量%,異氰酸基平均官能基數為3.4。對於所得之聚異氰酸酯組合物PA-b5,藉由H-NMR及C-NMR進行分析,確認縮二脲之存在。 The interior of a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube was replaced with nitrogen, and 1000 g of HDI, 7.2 g of water, and 600 g of ethylene glycol monomethyl ether acetate were mixed at room temperature and reacted at 140°C under normal pressure for 120 minutes. Then, the reaction was carried out at 160°C for 1 hour. No precipitate or turbidity was observed. After that, the reaction solution was filtered, and the unreacted HDI monomer and solvent were removed by a thin film distillation device to obtain polyisocyanate. The isocyanate content of the obtained polyisocyanate was 23.4% by mass, and the average functional group number of the isocyanate group was 3.4. The obtained polyisocyanate composition PA-b5 was analyzed by H-NMR and C-NMR to confirm the presence of biuret.

將實施例及比較例中所得之聚異氰酸酯組合物之物性、及利用上述記載之方法進行之評價之結果表示於以下表1~表3中。再者,於比較例1中,測定伸長率為140%時之應力時,未伸長至伸長率140%,斷裂點應力為73MPa,無法測定,因此,表中記為「-」。又,比較例4、5亦同樣如此。 The physical properties of the polyisocyanate compositions obtained in the examples and comparative examples, and the results of the evaluations performed using the above-described methods are shown in the following Tables 1 to 3. Furthermore, in Comparative Example 1, when the stress at an elongation of 140% was measured, the elongation was not elongated to 140%, and the stress at the fracture point was 73 MPa, which could not be measured, so it was marked as "-" in the table. The same is true for Comparative Examples 4 and 5.

又,於表1~表3中,各簡稱意指以下化合物。 In addition, in Tables 1 to 3, each abbreviation means the following compound.

(聚酯多元醇(A)) (Polyester polyol (A))

A1:二官能聚己內酯多元醇,Daicel公司製造,商品名「PLACCEL 220CPT」,數量平均分子量2000,羥值56.6mgKOH/g,酸值0.02mgKOH/g A1: Difunctional polycaprolactone polyol, manufactured by Daicel, trade name "PLACCEL 220CPT", number average molecular weight 2000, hydroxyl value 56.6 mgKOH/g, acid value 0.02 mgKOH/g

A2:二官能聚己內酯多元醇,Daicel公司製造,商品名「PLACCEL 230」,數量平均分子量3000,羥值37.6mgKOH/g,酸值0.07mgKOH/g A2: Difunctional polycaprolactone polyol, manufactured by Daicel, trade name "PLACCEL 230", number average molecular weight 3000, hydroxyl value 37.6 mgKOH/g, acid value 0.07 mgKOH/g

A3:二官能聚己內酯多元醇,Daicel公司製造,商品名「PLACCEL 240」,數量平均分子量4000,羥值28.5mgKOH/g,酸值0.07mgKOH/g A3: Difunctional polycaprolactone polyol, manufactured by Daicel, trade name "PLACCEL 240", number average molecular weight 4000, hydroxyl value 28.5mgKOH/g, acid value 0.07mgKOH/g

(其他二元多元醇(A')) (Other diols (A'))

A'1:聚四亞甲基醚二醇,三菱化學(股)製造,商品名「PTMG1000」,數量平均分子量1000 A'1: Polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Co., Ltd., trade name "PTMG1000", number average molecular weight 1000

A'2:聚醚多元醇,旭硝子(股)製造,商品名「Excenol2020」,數量平均分子量2000 A'2: Polyether polyol, manufactured by Asahi Glass Co., Ltd., trade name "Excenol 2020", number average molecular weight 2000

(聚酯多元醇(B)) (Polyester polyol (B))

B1:三官能聚己內酯多元醇,Daicel公司製造,商品名「PLACCEL 308」,數量平均分子量850,羥值195.3mgKOH/g,酸值0.38mgKOH/g B1: trifunctional polycaprolactone polyol, manufactured by Daicel, trade name "PLACCEL 308", number average molecular weight 850, hydroxyl value 195.3 mgKOH/g, acid value 0.38 mgKOH/g

B2:三官能聚己內酯多元醇,Daicel公司製造,商品名「PLACCEL 312」,數量平均分子量1250,羥值136.1mgKOH/g,酸值0.38mgKOH/g B2: trifunctional polycaprolactone polyol, manufactured by Daicel, trade name "PLACCEL 312", number average molecular weight 1250, hydroxyl value 136.1 mgKOH/g, acid value 0.38 mgKOH/g

B3:三官能聚己內酯多元醇,Daicel公司製造,商品名「PLACCEL 305」,數量平均分子量550 B3: trifunctional polycaprolactone polyol, manufactured by Daicel, trade name "PLACCEL 305", number average molecular weight 550

(其他三元多元醇(B')) (Other trihydric polyols (B'))

B'1:三羥甲基丙烷(TMP) B'1: Trihydroxymethylpropane (TMP)

Figure 111129090-A0305-02-0062-1
Figure 111129090-A0305-02-0062-1

Figure 111129090-A0305-02-0063-2
Figure 111129090-A0305-02-0063-2

Figure 111129090-A0305-02-0064-3
Figure 111129090-A0305-02-0064-3

Figure 111129090-A0305-02-0065-4
Figure 111129090-A0305-02-0065-4

如表1~表3所示,於由脂肪族或脂環族二異氰酸酯及具有特定之物性之聚酯多元醇(A)或聚酯多元醇(B)衍生且二異氰酸酯之異氰酸基相對於聚酯多元醇之羥基之莫耳比為特定之數值範圍內、且重量平均分子量為特定之數值範圍內的聚異氰酸酯組合物PA-a1~PA-a20(實施例1~20)中,獲得使聚異氰酸酯組合物單獨硬化而成之硬化膜之硬度較低且柔軟性及透明性良好、伸長率為140%時之應力較低且伸長率及拉伸斷裂應力較高並 且耐彎曲性優異之硬化膜,以及黏著力、硬化性及透明性優異之黏著性樹脂片材。 As shown in Tables 1 to 3, in the polyisocyanate compositions PA-a1 to PA-a20 (Examples 1 to 20) derived from aliphatic or alicyclic diisocyanates and polyester polyols (A) or polyester polyols (B) having specific physical properties, in which the molar ratio of the isocyanate group of the diisocyanate to the hydroxyl group of the polyester polyol is within a specific numerical range and the weight average molecular weight is within a specific numerical range, a cured film obtained by curing the polyisocyanate composition alone has low hardness, good flexibility and transparency, low stress at 140% elongation, high elongation and tensile fracture stress, and excellent bending resistance, and an adhesive resin sheet with excellent adhesion, curability and transparency is obtained.

與此相對,如表4所示,於由二異氰酸酯及不具有上述物性之多元醇衍生之聚異氰酸酯組合物PA-b1~PA-b5(比較例1~5)中,無法獲得使聚異氰酸酯組合物單獨硬化而成之硬化膜1之硬度及透明性、製成硬化膜2時之伸長率為140%時之應力、伸長率及拉伸斷裂應力、以及製成黏著性樹脂片材時之黏著性、硬化性及透明性均優異者。 In contrast, as shown in Table 4, in the polyisocyanate compositions PA-b1 to PA-b5 (Comparative Examples 1 to 5) derived from diisocyanate and polyols not having the above-mentioned properties, it is not possible to obtain the hardness and transparency of the cured film 1 formed by curing the polyisocyanate composition alone, the stress, elongation and tensile fracture stress when the elongation is 140% when the cured film 2 is made, and the adhesion, curability and transparency when the adhesive resin sheet is made are all excellent.

[產業上之可利用性] [Industrial availability]

根據本實施方式之聚異氰酸酯組合物,能夠提供一種聚異氰酸酯組合物,其能夠獲得使聚異氰酸酯組合物單獨硬化而成之硬化膜之柔軟性及透明性良好且伸長率及拉伸斷裂應力優異之硬化膜、以及黏著力、硬化性及透明性優異之黏著性樹脂組合物及黏著性樹脂片材。又,本發明能夠提供一種具備上述黏著性樹脂片材之積層膜。 According to the polyisocyanate composition of this embodiment, a polyisocyanate composition can be provided, which can obtain a cured film formed by curing the polyisocyanate composition alone, which has good softness and transparency, and excellent elongation and tensile fracture stress, as well as an adhesive resin composition and an adhesive resin sheet with excellent adhesion, curability and transparency. In addition, the present invention can provide a laminated film having the above-mentioned adhesive resin sheet.

Claims (23)

一種聚異氰酸酯組合物,其係由選自由脂肪族二異氰酸酯及脂環族二異氰酸酯所組成之群中之至少1種二異氰酸酯、及選自由數量平均分子量Mn為500以上之二官能聚酯多元醇(A)及數量平均分子量Mn為500以上之三官能以上之聚酯多元醇(B)所組成之群中之至少1種聚酯多元醇衍生,上述二異氰酸酯之異氰酸基相對於上述聚酯多元醇之羥基之莫耳比為1.5以上30.0以下,上述聚異氰酸酯組合物之重量平均分子量為3000以上800000以下。 A polyisocyanate composition is derived from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and at least one polyester polyol selected from the group consisting of a difunctional polyester polyol (A) having a number average molecular weight Mn of 500 or more and a trifunctional or higher polyester polyol (B) having a number average molecular weight Mn of 500 or more, wherein the molar ratio of the isocyanate group of the diisocyanate to the hydroxyl group of the polyester polyol is 1.5 or more and 30.0 or less, and the weight average molecular weight of the polyisocyanate composition is 3000 or more and 800000 or less. 如請求項1之聚異氰酸酯組合物,其中上述聚異氰酸酯組合物之平均異氰酸基官能基數為2.0以上6.0以下。 As in claim 1, the polyisocyanate composition, wherein the average number of isocyanate functional groups of the polyisocyanate composition is greater than 2.0 and less than 6.0. 如請求項1或2之聚異氰酸酯組合物,其中上述聚異氰酸酯組合物之異氰酸基含有率為1.0質量%以上8.7質量%以下。 The polyisocyanate composition of claim 1 or 2, wherein the isocyanate group content of the polyisocyanate composition is greater than 1.0 mass % and less than 8.7 mass %. 如請求項1或2之聚異氰酸酯組合物,其中相對於上述二異氰酸酯100質量份,上述聚酯多元醇(A)之含量為0.1質量份以上900質量份以下,相對於上述二異氰酸酯100質量份,上述聚酯多元醇(B)之含量為0.1質量份以上900質量份以下。 The polyisocyanate composition of claim 1 or 2, wherein the content of the polyester polyol (A) is 0.1 to 900 parts by mass relative to 100 parts by mass of the diisocyanate, and the content of the polyester polyol (B) is 0.1 to 900 parts by mass relative to 100 parts by mass of the diisocyanate. 如請求項1或2之聚異氰酸酯組合物,其中上述聚酯多元醇係聚己內 酯多元醇。 The polyisocyanate composition of claim 1 or 2, wherein the polyester polyol is polycaprolactone polyol. 如請求項1或2之聚異氰酸酯組合物,其塗敷於玻璃上並於23℃、65%濕度環境下保管168小時後形成之膜厚為40μm之硬化膜於23℃環境下之柯尼希硬度為60次以下。 For example, the polyisocyanate composition of claim 1 or 2 is applied on glass and stored in an environment of 23°C and 65% humidity for 168 hours to form a cured film with a thickness of 40 μm, and a Koenig hardness of less than 60 times in an environment of 23°C. 如請求項6之聚異氰酸酯組合物,其中於將膜厚為40μm之上述硬化膜貼附於霧度值為0.1%之玻璃上之狀態下藉由霧度計測定之霧度值為3.0%以下。 The polyisocyanate composition of claim 6, wherein the haze value measured by a haze meter when the above-mentioned cured film having a film thickness of 40 μm is attached to a glass having a haze value of 0.1% is less than 3.0%. 一種硬化膜,其係包含如請求項1或2之聚異氰酸酯組合物、及玻璃轉移溫度為0℃以上100℃以下之多元醇的樹脂組合物之硬化膜,以速度20mm/分鐘測定之拉伸試驗中之伸長率為140%以上,伸長率為140%時之應力為25.0MPa以下,且拉伸斷裂應力為上述伸長率為140%時之應力之1.2倍以上。 A cured film comprising a polyisocyanate composition as claimed in claim 1 or 2 and a polyol resin composition having a glass transition temperature of 0°C or higher and 100°C or lower, wherein the elongation in a tensile test measured at a speed of 20 mm/min is 140% or higher, the stress at 140% is 25.0 MPa or lower, and the tensile fracture stress is 1.2 times or more of the stress at 140% above. 如請求項8之硬化膜,其中相對於上述多元醇100質量份,上述聚異氰酸酯組合物之含量為0.01質量份以上200質量份以下。 For example, in the cured film of claim 8, the content of the polyisocyanate composition is not less than 0.01 parts by mass and not more than 200 parts by mass relative to 100 parts by mass of the polyol. 一種黏著性樹脂組合物,其包含如請求項1或2之聚異氰酸酯組合物、及玻璃轉移溫度為0.0℃以下之含有交聯性官能基之聚合物。 An adhesive resin composition comprising a polyisocyanate composition as claimed in claim 1 or 2, and a polymer containing a crosslinking functional group having a glass transition temperature of 0.0°C or less. 如請求項10之黏著性樹脂組合物,其中上述含有交聯性官能基之聚 合物係丙烯酸系聚合物或胺基甲酸酯系聚合物。 As in claim 10, the adhesive resin composition, wherein the polymer containing the cross-linking functional group is an acrylic polymer or a urethane polymer. 如請求項10之黏著性樹脂組合物,其中上述含有交聯性官能基之聚合物係使具有交聯性官能基之聚合性(甲基)丙烯酸單體、與酯基末端之碳數為1以上18以下之(甲基)丙烯酸酯單體共聚而成,且玻璃轉移溫度Tg為-75.0℃以上0.0℃以下。 As in claim 10, the adhesive resin composition, wherein the polymer containing crosslinking functional groups is obtained by copolymerizing a polymerizable (meth) acrylic monomer having a crosslinking functional group and a (meth) acrylic ester monomer having an ester terminal with a carbon number of 1 to 18, and the glass transition temperature Tg is above -75.0℃ and below 0.0℃. 如請求項10之黏著性樹脂組合物,其中上述含有交聯性官能基之聚合物之重量平均分子量為1.0×105以上5.0×106以下。 The adhesive resin composition of claim 10, wherein the weight average molecular weight of the polymer containing the crosslinking functional group is 1.0×10 5 or more and 5.0×10 6 or less. 如請求項10之黏著性樹脂組合物,其中上述交聯性官能基係選自由羥基、環氧基、氧雜環丁基、羧基、乙烯基、及胺基所組成之群中之1種以上。 As in claim 10, the adhesive resin composition, wherein the cross-linking functional group is selected from at least one of the group consisting of hydroxyl, epoxy, cyclobutyl, carboxyl, vinyl, and amino. 如請求項10之黏著性樹脂組合物,其中相對於上述含有交聯性官能基之聚合物100質量份,上述聚異氰酸酯組合物之含量為0.01質量份以上20.00質量份以下。 As in claim 10, the adhesive resin composition, wherein the content of the polyisocyanate composition is not less than 0.01 parts by mass and not more than 20.00 parts by mass relative to 100 parts by mass of the polymer containing the crosslinking functional group. 一種黏著性樹脂片材,其係使如請求項10之黏著性樹脂組合物藉由熱或光發生硬化而成。 An adhesive resin sheet is formed by hardening the adhesive resin composition of claim 10 by heat or light. 如請求項16之黏著性樹脂片材,其中上述黏著性樹脂片材之厚度為1μm以上1000μm以下。 As in claim 16, the adhesive resin sheet has a thickness of not less than 1 μm and not more than 1000 μm. 如請求項16之黏著性樹脂片材,其凝膠分率為20.0質量%以上99.9質量%以下。 For example, the adhesive resin sheet in claim 16 has a gel fraction of 20.0% by mass and less than 99.9% by mass. 如請求項16之黏著性樹脂片材,其於23℃下以300mm/分鐘之速度測定之180度剝離黏著力為0.05N/20mm以上65.00N/20mm以下。 For example, the adhesive resin sheet of claim 16 has a 180-degree peeling adhesion measured at 23°C at a speed of 300 mm/min of not less than 0.05 N/20 mm and not more than 65.00 N/20 mm. 如請求項16之黏著性樹脂片材,其將厚度50μm之黏著性樹脂片材貼附於霧度值為0.1%之玻璃上並藉由霧度計測定之霧度值為2.0%以下。 For example, the adhesive resin sheet of claim 16, wherein the adhesive resin sheet with a thickness of 50 μm is attached to glass with a haze value of 0.1% and the haze value measured by a haze meter is less than 2.0%. 一種積層膜,其係於如請求項16之黏著性樹脂片材之至少一個面上積層有膜基材者。 A laminated film, which is a film substrate laminated on at least one surface of the adhesive resin sheet as claimed in claim 16. 如請求項21之積層膜,其中上述膜基材係選自由聚酯系樹脂、乙酸酯系樹脂、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、(甲基)丙烯酸系樹脂、聚氯乙烯系樹脂、聚偏二氯乙烯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、聚芳酯系樹脂、聚苯硫醚系樹脂、三乙醯纖維素系樹脂所組成之群中之至少1種。 The laminated film of claim 21, wherein the film substrate is at least one selected from the group consisting of polyester resins, acetate resins, polyether sulfide resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, and triacetyl cellulose resins. 如請求項21之積層膜,其中上述積層膜用於光學用途。The multilayer film of claim 21, wherein the multilayer film is used for optical purposes.
TW111129090A 2021-08-10 2022-08-03 Polyisocyanate composition, cured film, adhesive resin composition, adhesive resin sheet, and laminated film TWI839801B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-130608 2021-08-10
JP2021130608 2021-08-10

Publications (2)

Publication Number Publication Date
TW202313748A TW202313748A (en) 2023-04-01
TWI839801B true TWI839801B (en) 2024-04-21

Family

ID=85200612

Family Applications (1)

Application Number Title Priority Date Filing Date
TW111129090A TWI839801B (en) 2021-08-10 2022-08-03 Polyisocyanate composition, cured film, adhesive resin composition, adhesive resin sheet, and laminated film

Country Status (5)

Country Link
JP (1) JPWO2023017835A1 (en)
KR (1) KR20240028493A (en)
CN (1) CN117794973A (en)
TW (1) TWI839801B (en)
WO (1) WO2023017835A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200728340A (en) * 2005-08-05 2007-08-01 Bayer Materialscience Llc Low surface energy polyisocyanates and their use in two-component coating compositions
JP2017170658A (en) * 2016-03-19 2017-09-28 三菱ケミカル株式会社 Laminate film
JP2020090588A (en) * 2018-12-04 2020-06-11 旭化成株式会社 Polyisocyanate composition, coating composition, and coating film

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6128518A (en) * 1984-07-20 1986-02-08 Asahi Chem Ind Co Ltd Production of prepolymer for ductile polyurethane coating
DE3703973A1 (en) * 1987-02-10 1988-08-18 Bayer Ag PROCESS FOR THE PREPARATION OF PRE-POLYMERS HAVING ISOCYANATE GROUPS, THE PRE-POLYMERS PREPARED THEREOF AND THEIR USE
JPH021718A (en) 1988-02-01 1990-01-08 Asahi Chem Ind Co Ltd Urethane prepolymer and polyurethane coating composition
EP1706440A1 (en) * 2004-01-14 2006-10-04 Cytec Surface Specialties, S.A. Adhesives
JP2016089034A (en) * 2014-11-05 2016-05-23 Dic株式会社 Polyester polyisocyanate, curing agent for two-liquid type urethane adhesive using the same, two-liquid type urethane adhesive, laminate film and back sheet for solar battery
CN110382644B (en) * 2017-03-07 2022-04-19 旭化成株式会社 Polyaspartic acid coating composition, coating film, and coated article
JP7261611B2 (en) * 2019-02-27 2023-04-20 旭化成株式会社 Polyisocyanate composition, coating composition and coating film
CN113939552B (en) * 2019-08-01 2024-01-30 旭化成株式会社 Blocked polyisocyanate composition, one-component coating composition, coating film and coated article

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200728340A (en) * 2005-08-05 2007-08-01 Bayer Materialscience Llc Low surface energy polyisocyanates and their use in two-component coating compositions
JP2017170658A (en) * 2016-03-19 2017-09-28 三菱ケミカル株式会社 Laminate film
JP2020090588A (en) * 2018-12-04 2020-06-11 旭化成株式会社 Polyisocyanate composition, coating composition, and coating film

Also Published As

Publication number Publication date
WO2023017835A1 (en) 2023-02-16
KR20240028493A (en) 2024-03-05
CN117794973A (en) 2024-03-29
TW202313748A (en) 2023-04-01
JPWO2023017835A1 (en) 2023-02-16

Similar Documents

Publication Publication Date Title
TWI512075B (en) Composition of photohardenable transparent adhesive sheet
KR101234849B1 (en) Adhesive composition and optical member using the same
CN106795414B (en) Adhesive composition, adhesive layer, optical member using the same, and image display device
TW201339266A (en) Adhesive composition and adhesive sheet
TW201610014A (en) Active-energy-curing resin composition, coating material, coating film, and laminate film
JP6241677B2 (en) Undercoat agent for substrate with copper thin film, substrate with copper thin film and method for producing the same, and conductive film and electrode film
TWI702240B (en) Urethane (meth)acrylate resin and laminated film
TWI848450B (en) Polyisocyanate composition, hardened film, coating film, adhesive composition, adhesive sheet and resin composition
TWI839801B (en) Polyisocyanate composition, cured film, adhesive resin composition, adhesive resin sheet, and laminated film
KR102494970B1 (en) Adhesive Composition and Adhesive Sheet Using the Same
JP6705276B2 (en) Urethane (meth)acrylate resin and laminated film
JP2015189799A (en) Curable resin composition, hard coat material and cured product
KR102446328B1 (en) Adhesive Composition and Adhesive Sheet Using the Same
KR102713627B1 (en) Optical resin composition and optical resin sheet
TWI663471B (en) Active energy ray-curable resin composition, cured product, adhesive, and laminated film
CN111548761B (en) Adhesive composition for polarizing plate, polarizing plate with adhesive layer, and in-vehicle display device
JP2022156488A (en) Pressure sensitive adhesive resin composition for surface-protecting film and surface-protecting film
JP2023171322A (en) resin film
CN109312047A (en) Carbamate (methyl) acrylate and laminate film
TW202330669A (en) Optical adhesive, and adhesive sheet
JP2022081414A (en) Polyisocyanate composition, cured film, coating film, adhesive composition and adhesive sheet
JP2022159124A (en) Optical resin composition and optical resin sheet
JP2023170006A (en) Adhesive resin composition, and adhesive resin sheet
JP2017002104A (en) Urethane (meth)acrylate resin and laminated film
JP6718131B2 (en) Urethane (meth)acrylate resin and laminated film