TW202026385A - Adhesive composition for surface protection sheet and surface protective sheet - Google Patents
Adhesive composition for surface protection sheet and surface protective sheet Download PDFInfo
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- TW202026385A TW202026385A TW108134335A TW108134335A TW202026385A TW 202026385 A TW202026385 A TW 202026385A TW 108134335 A TW108134335 A TW 108134335A TW 108134335 A TW108134335 A TW 108134335A TW 202026385 A TW202026385 A TW 202026385A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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Abstract
Description
本發明係有關表面保護薄片用黏著劑組成物及表面保護薄片,特別是有關包含具有(甲基)丙烯醯基之化合物的表面保護薄片用黏著劑組成物,及具有此表面保護薄片用黏著劑組成物之硬化物的表面保護薄片。The present invention relates to an adhesive composition for a surface protection sheet and a surface protection sheet, and particularly relates to an adhesive composition for a surface protection sheet containing a compound having a (meth)acryloyl group, and an adhesive for the surface protection sheet The surface protection sheet of the hardened material of the composition.
智慧型手機、個人電腦、電視等之液晶顯示器或觸控面板等的光學元件使用了各種的光學薄膜。此等光學薄膜的表面為了防止在輸送步驟、製造步驟、檢查步驟之污染或受傷之目的,一般被積層保護薄片(表面保護薄片)。此保護薄片在組裝步驟等之後步驟被剝離。這種作為保護薄片用之黏著劑,提案了各種胺基甲酸酯黏著劑。Various optical films are used for optical components such as liquid crystal displays or touch panels of smart phones, personal computers, and televisions. The surface of these optical films is generally laminated with a protective sheet (surface protective sheet) for the purpose of preventing contamination or damage during the conveying, manufacturing, and inspection steps. This protective sheet is peeled off after the assembly step and the like. Various urethane adhesives have been proposed as adhesives for protective sheets.
例如,專利文獻1中記載一種透明黏著薄片用光硬化性組成物,其係包含以聚氧伸烷基多元醇為骨架,且在末端具有(甲基)丙烯醯基之重量平均分子量為1萬~30萬之聚胺基甲酸酯、具有羥基之(甲基)丙烯酸酯、其他的光聚合性單體及光聚合起始劑。For example, Patent Document 1 describes a photocurable composition for a transparent adhesive sheet, which contains a polyoxyalkylene polyol as a skeleton and has a (meth)acryloyl group at the end with a weight average molecular weight of 10,000. ~300,000 polyurethanes, (meth)acrylates with hydroxyl groups, other photopolymerizable monomers and photopolymerization initiators.
又,專利文獻2中記載一種透明黏著薄片用光硬化性組成物,其係含有在聚氧伸烷基鏈之末端經由胺基甲酸酯鍵,鍵結有(甲基)丙烯醯基之聚胺基甲酸酯、具有羥基之(甲基)丙烯酸酯、具有芳香環之(甲基)丙烯酸酯、其他的聚合性單體及光聚合起始劑。In addition, Patent Document 2 describes a photocurable composition for a transparent adhesive sheet, which contains a polyoxyalkylene chain terminal via a urethane bond to which a (meth)acrylic acid group is bonded. Urethane, (meth)acrylate having a hydroxyl group, (meth)acrylate having an aromatic ring, other polymerizable monomers, and photopolymerization initiators.
光學元件之檢查步驟中,在製品或零件上積層有保護薄片的狀態下,有要求充分地發現或可檢測製品或零件之微細的異物或受傷的情形。因此,對於保護薄片要求濁度少,亦即霧度低。In the inspection step of optical components, in the state where the protective sheet is laminated on the product or part, it is required to fully detect or detect the fine foreign matter or injury of the product or part. Therefore, the protective sheet is required to have low haze, that is, low haze.
又,光學元件之製造步驟,保護薄片有重複積層與剝離的情形。因此,對保護薄片要求對被黏物之積層容易度(對被黏物之高的潤濕性)、及剝離容易度。又,最近,隨著顯示器之大畫面化、面板零件等之薄膜化,光學元件本身變成容易龜裂。因此,對保護薄片有要求具有適度的黏著性(剝離強度),同時可以更輕的力量剝離(輕剝離性)。此外,也要求不會發生在保護薄片之剝離後,對製品表面(被黏物)之黏著劑層之一部分等殘留即所謂的黏著劑殘留(再剝離性)。 [先前技術文獻] [專利文獻]In addition, in the manufacturing process of the optical element, the protective sheet may be repeatedly laminated and peeled off. Therefore, the protection sheet requires the ease of stacking the adherend (high wettability to the adherend) and the ease of peeling. In addition, recently, as the display screen becomes larger and the panel parts become thinner, the optical element itself becomes prone to cracks. Therefore, the protective sheet is required to have moderate adhesion (peel strength), and at the same time, it can be peeled off with a lighter force (light peelability). In addition, it is also required that the so-called adhesive residue (re-peelability) does not occur after the peeling of the protective sheet and a part of the adhesive layer on the surface of the product (adhesive). [Prior Technical Literature] [Patent Literature]
[專利文獻1] 日本特開2014-210895號公報 [專利文獻2] 日本特開2016-20477號公報[Patent Document 1] JP 2014-210895 A [Patent Document 2] JP 2016-20477 A
[發明所欲解決之課題][The problem to be solved by the invention]
但是專利文獻1及專利文獻2所記載之組成物,並非以使用於製造步驟剝離用之保護薄片為目的者,使用了此等組成物的黏著薄片,其剝離強度高。However, the composition described in Patent Document 1 and Patent Document 2 is not intended to be used as a protective sheet for peeling in the manufacturing process, and an adhesive sheet using these compositions has high peel strength.
因此,本發明人為了解決上述課題而精心檢討,藉由使包含:具有包含來自聚氧伸烷基多元醇及來自聚異氰酸酯之結構的骨架,且包含在複數末端具有(甲基)丙烯醯基之聚胺基甲酸酯的重量平均分子量為30,000~200,000之聚胺基甲酸酯;具有複數(甲基)丙烯醯基之多官能單體;可與聚胺基甲酸酯及多官能單體聚合之其他的單體;及光聚合起始劑的光硬化性表面保護薄片用黏著劑組成物硬化,可得到霧度低,容易積層,容易剝離,及可抑制剝離後之黏著劑殘留的表面保護薄片。但是由此光硬化性表面保護薄片用黏著劑組成物所得的表面保護薄片,因黏著劑層稍微硬,故得知使黏著劑層變厚的薄片進行雷射切割或刀切割時,黏著劑層之端面發生龜裂的情形。Therefore, in order to solve the above-mentioned problems, the present inventors conducted a careful review by including: a skeleton having a structure derived from polyoxyalkylene polyol and polyisocyanate, and including a (meth)acryloyl group at plural ends Polyurethane with a weight average molecular weight of 30,000~200,000; a polyfunctional monomer with plural (meth)acrylic groups; can be combined with polyurethane and polyfunctional mono Other monomers that are polymerized in bulk; and the adhesive composition for photocurable surface protection sheets of photopolymerization initiator is hardened to obtain low haze, easy build-up, easy peeling, and can prevent adhesive residue after peeling Surface protection sheet. However, the surface protection sheet obtained from the adhesive composition for photocurable surface protection sheet has a slightly harder adhesive layer. Therefore, it is known that the adhesive layer is Cracks occurred on the end face.
因此,本發明之目的係提供除了霧度低,容易積層,容易剝離,可抑制剝離後之黏著劑殘留,且切斷加工時黏著劑層不會產生龜裂之表面保護薄片用的表面保護薄片用黏著劑組成物。又,本發明之另1個目的係提供除了霧度低,容易積層,容易剝離,可抑制剝離後之黏著劑殘留外,且切斷加工時黏著劑層不會產生龜裂之表面保護薄片。 [用以解決課題之手段]Therefore, the object of the present invention is to provide a surface protection sheet for a surface protection sheet that has low haze, is easy to build up, easy to peel, can prevent adhesive residue after peeling, and does not crack the adhesive layer during cutting processing Use adhesive composition. In addition, another object of the present invention is to provide a surface protection sheet that has low haze, is easy to build up, is easy to peel, can prevent adhesive residue after peeling, and does not crack the adhesive layer during cutting. [Means to solve the problem]
為了解決上述課題用之本發明之構成係如下述。 [1]一種表面保護薄片用黏著劑組成物,其係包含聚胺基甲酸酯(A)、多官能單體(B)、可與聚胺基甲酸酯(A)及多官能單體(B)聚合的其他的單體(C)及光聚合起始劑(D)的表面保護薄片用黏著劑組成物, 其中前述聚胺基甲酸酯(A)為具有包含來自聚氧伸烷基多元醇之結構及來自聚異氰酸酯之結構之骨架的聚胺基甲酸酯, 前述聚胺基甲酸酯(A)包含聚胺基甲酸酯(a1), 前述聚胺基甲酸酯(a1)具有包含來自聚氧伸烷基多元醇之結構及來自聚異氰酸酯之結構的骨架,且前述聚胺基甲酸酯(a1)之複數的末端具有(甲基)丙烯醯基, 前述聚胺基甲酸酯(A)之重量平均分子量為30,000~ 200,000, 前述多官能單體(B)為具有複數之(甲基)丙烯醯基的化合物, 相對於前述聚胺基甲酸酯(A)與前述多官能單體(B)與前述其他的單體(C)之總量100質量%, 前述聚胺基甲酸酯(A)之含量為30~60質量%, 前述多官能單體(B)之含量為2~10質量%, 前述其他的單體(C)之含量為30~68質量%, 相對於前述聚胺基甲酸酯(A)與前述多官能單體(B)與前述其他的單體(C)之總量100質量份, 光聚合起始劑(D)之含量為0.1~5質量份。 [2]如[1]之表面保護薄片用黏著劑組成物,其中前述聚胺基甲酸酯(A)所含有之來自前述聚氧伸烷基多元醇之結構為來自數平均分子量500~5,000之聚氧伸烷基多元醇的結構。 [3]如[1]或[2]之表面保護薄片用黏著劑組成物,其中前述聚胺基甲酸酯(A)所含有之前述骨架為聚氧烷二醇及二異氰酸酯之共聚物。 [4]如[1]~[3]中任一項之表面保護薄片用黏著劑組成物,其中前述聚氧烷二醇為聚丙二醇, 前述二異氰酸酯為二苯基甲烷二異氰酸酯的氫化物。 [5]如[1]~[4]中任一項之表面保護薄片用黏著劑組成物,其中前述聚胺基甲酸酯(A)中之前述(甲基)丙烯醯基為(甲基)丙烯醯氧基之一部分。 [6]如[1]~[5]中任一項之表面保護薄片用黏著劑組成物,其中前述多官能單體(B)具有3個以上之(甲基)丙烯醯基。 [7]如[6]之表面保護薄片用黏著劑組成物,其中前述多官能單體(B)為三羥甲基丙烷三丙烯酸酯。 [8]如[7]之表面保護薄片用黏著劑組成物,其中前述其他的單體(C)具有(甲基)丙烯醯基。 [9]如[8]之表面保護薄片用黏著劑組成物,其中前述其他的單體(C)包含烷基(甲基)丙烯酸酯。 [10]如[1]~[9]中任一項之表面保護薄片用黏著劑組成物,其中前述聚胺基甲酸酯(A)進一步包含聚胺基甲酸酯(a2), 前述聚胺基甲酸酯(a2)包含:具有包含來自聚氧伸烷基多元醇及聚異氰酸酯之結構的骨架,且僅前述聚胺基甲酸酯(a2)之任一個末端具有(甲基)丙烯醯基的聚胺基甲酸酯(a2)。 [11]如[1]~[10]中任一項之表面保護薄片用黏著劑組成物,其中以數基準,在前述聚胺基甲酸酯(A)所含有之聚胺基甲酸酯分子之末端的90~100%被導入(甲基)丙烯醯基。 [12]一種表面保護薄片,其係具有薄片狀的基材,及形成於前述基材上的黏著劑層, 其中前述黏著劑層為由如[1]~[11]中任一項之表面保護薄片用黏著劑組成物之光硬化物所成者。 [發明效果]The structure of the present invention for solving the above-mentioned problems is as follows. [1] An adhesive composition for a surface protection sheet, which contains polyurethane (A), a polyfunctional monomer (B), and can be combined with polyurethane (A) and a polyfunctional monomer (B) An adhesive composition for surface protection sheets of polymerized other monomers (C) and photopolymerization initiator (D), Wherein the aforementioned polyurethane (A) is a polyurethane having a skeleton containing a structure derived from polyoxyalkylene polyol and a structure derived from polyisocyanate, The aforementioned polyurethane (A) includes polyurethane (a1), The aforementioned polyurethane (a1) has a skeleton containing a structure derived from polyoxyalkylene polyol and a structure derived from polyisocyanate, and the plural ends of the aforementioned polyurethane (a1) have (methyl ) Acrylic, The weight average molecular weight of the aforementioned polyurethane (A) is 30,000~200,000, The aforementioned polyfunctional monomer (B) is a compound having plural (meth)acrylic groups, 100% by mass relative to the total amount of the polyurethane (A), the polyfunctional monomer (B), and the other monomer (C), The content of the aforementioned polyurethane (A) is 30-60% by mass, The content of the aforementioned multifunctional monomer (B) is 2-10% by mass, The content of the aforementioned other monomer (C) is 30~68% by mass, With respect to 100 parts by mass of the total amount of the polyurethane (A), the polyfunctional monomer (B), and the other monomer (C), The content of the photopolymerization initiator (D) is 0.1 to 5 parts by mass. [2] The adhesive composition for a surface protection sheet according to [1], wherein the structure derived from the polyoxyalkylene polyol contained in the polyurethane (A) is derived from a number average molecular weight of 500 to 5,000 The structure of polyoxyalkylene polyol. [3] The adhesive composition for a surface protection sheet according to [1] or [2], wherein the skeleton contained in the polyurethane (A) is a copolymer of polyoxyalkylene glycol and diisocyanate. [4] The adhesive composition for a surface protection sheet according to any one of [1] to [3], wherein the aforementioned polyoxyalkylene glycol is polypropylene glycol, The aforementioned diisocyanate is a hydrogenated product of diphenylmethane diisocyanate. [5] The adhesive composition for a surface protection sheet according to any one of [1] to [4], wherein the (meth)acryloyl group in the polyurethane (A) is (methyl) ) A part of the propylene oxy group. [6] The adhesive composition for a surface protection sheet according to any one of [1] to [5], wherein the multifunctional monomer (B) has 3 or more (meth)acrylic groups. [7] The adhesive composition for a surface protection sheet according to [6], wherein the multifunctional monomer (B) is trimethylolpropane triacrylate. [8] The adhesive composition for a surface protection sheet according to [7], wherein the aforementioned other monomer (C) has a (meth)acryloyl group. [9] The adhesive composition for a surface protection sheet according to [8], wherein the aforementioned other monomer (C) contains an alkyl (meth)acrylate. [10] The adhesive composition for a surface protection sheet according to any one of [1] to [9], wherein the aforementioned polyurethane (A) further comprises polyurethane (a2), The aforementioned polyurethane (a2) comprises: a skeleton having a structure derived from polyoxyalkylene polyol and polyisocyanate, and only any one end of the aforementioned polyurethane (a2) has (methyl) ) Acrylic-based polyurethane (a2). [11] The adhesive composition for a surface protection sheet according to any one of [1] to [10], wherein, on a numerical basis, the polyurethane contained in the aforementioned polyurethane (A) 90-100% of the end of the molecule is introduced into (meth)acrylic acid groups. [12] A surface protection sheet, which has a sheet-like substrate and an adhesive layer formed on the substrate, Wherein, the aforementioned adhesive layer is formed by the photocured material of the adhesive composition for surface protection sheet as in any one of [1] to [11]. [Invention Effect]
依據本發明時,可提供除了霧度低,容易積層,容易剝離,可抑制剝離後之黏著劑殘留,且切斷加工時黏著劑層不會產生龜裂之表面保護薄片用的表面保護薄片用黏著劑組成物。又,依據本發明時,可提供除了霧度低,容易積層,容易剝離,可抑制剝離後之黏著劑殘留外,切斷加工時黏著劑層不會產生龜裂之表面保護薄片。According to the present invention, it is possible to provide a surface protection sheet for a surface protection sheet that has low haze, is easy to build up, and is easy to peel off, can suppress the adhesive residue after peeling, and the adhesive layer does not crack during cutting processing. Adhesive composition. In addition, according to the present invention, it is possible to provide a surface protection sheet that has low haze, is easy to build up, easy to peel, and can prevent adhesive residue after peeling, and does not crack the adhesive layer during cutting.
[實施發明之形態][The form of implementing the invention]
以下說明本發明之一實施形態。在此,(甲基)丙烯醯基係指選自以化學式CH2 =CH-CO-表示之基團、及以化學式CH2 =C(CH3 )-CO-表示之官能基之一種以上,(甲基)丙烯醯氧基係指選自以化學式CH2 =CH-CO-O-表示之基團、及以化學式CH2 =C(CH3 )-CO-O-表示之官能基之一種以上。又,異氰酸酯基係指以化學式-N=C=O表示之官能基。An embodiment of the present invention will be described below. Here, the (meth)acryloyl group refers to one or more selected from the group represented by the chemical formula CH 2 =CH-CO- and the functional group represented by the chemical formula CH 2 =C(CH 3 )-CO-, The (meth)acryloxy group refers to a group selected from the group represented by the chemical formula CH 2 =CH-CO-O- and the functional group represented by the chemical formula CH 2 =C(CH 3 )-CO-O- the above. In addition, the isocyanate group refers to a functional group represented by the chemical formula -N=C=O.
<1.表面保護薄片用黏著劑組成物> 本實施形態之表面保護薄片用黏著劑組成物(以下有時稱為「黏著劑組成物」)係包含聚胺基甲酸酯(A)、多官能單體(B)、可與聚胺基甲酸酯(A)及多官能單體(B)聚合的其他的單體(C)及光聚合起始劑(D)。前述聚胺基甲酸酯(A)為具有包含來自聚氧伸烷基多元醇之結構及來自聚異氰酸酯之結構之骨架的聚胺基甲酸酯。前述聚胺基甲酸酯(A)包含聚胺基甲酸酯(a1)。前述聚胺基甲酸酯(a1)為具有包含來自聚氧伸烷基多元醇之結構及來自聚異氰酸酯之結構之骨架,且前述聚胺基甲酸酯(a1)之複數的末端具有(甲基)丙烯醯基。前述聚胺基甲酸酯(A)之重量平均分子量為30,000~200,000。前述多官能單體(B)為具有複數(甲基)丙烯醯基的化合物。相對於前述聚胺基甲酸酯(A)與前述多官能單體(B)與前述其他的單體(C)之總量100質量%,前述聚胺基甲酸酯(A)之含量為30~60質量%,前述多官能單體(B)之含量為2~10質量%,前述其他的單體(C)之含量為30~68質量%。又,相對於前述聚胺基甲酸酯(A)與前述多官能單體(B)與前述其他的單體(C)之總量100質量份,光聚合起始劑(D)之含量為0.1~5質量份為特徵。 又,本實施形態之黏著劑組成物,必要時,也可含有脂肪酸酯等的添加劑。此外,本實施形態之黏著劑組成物,也可不含溶劑,必要時,也可含有溶劑。 以下說明黏著劑組成物所含有的各成分。又,以下之說明中,由聚胺基甲酸酯(A)、多官能單體(B)、及其他的單體(C)所成的成分有時稱為「成分(A)~(C)」。<1. Adhesive composition for surface protection sheet> The adhesive composition for surface protection sheets of this embodiment (hereinafter sometimes referred to as "adhesive composition") contains polyurethane (A), polyfunctional monomer (B), and a Other monomers (C) and photopolymerization initiator (D) in which the formate (A) and the polyfunctional monomer (B) are polymerized. The aforementioned polyurethane (A) is a polyurethane having a skeleton including a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate. The aforementioned polyurethane (A) includes polyurethane (a1). The aforementioned polyurethane (a1) has a skeleton comprising a structure derived from polyoxyalkylene polyol and a structure derived from polyisocyanate, and the plural ends of the aforementioned polyurethane (a1) have (former Base) Acrylic acid base. The weight average molecular weight of the aforementioned polyurethane (A) is 30,000 to 200,000. The aforementioned polyfunctional monomer (B) is a compound having plural (meth)acrylic groups. The content of the polyurethane (A) is 100% by mass relative to the total amount of the polyurethane (A), the polyfunctional monomer (B), and the other monomer (C) 30-60% by mass, the content of the aforementioned multifunctional monomer (B) is 2-10% by mass, and the content of the aforementioned other monomer (C) is 30-68% by mass. In addition, the content of the photopolymerization initiator (D) relative to 100 parts by mass of the total amount of the polyurethane (A), the polyfunctional monomer (B), and the other monomer (C) is 0.1 to 5 parts by mass is characteristic. In addition, the adhesive composition of the present embodiment may contain additives such as fatty acid esters if necessary. In addition, the adhesive composition of this embodiment may not contain a solvent, and may contain a solvent if necessary. The components contained in the adhesive composition will be described below. In addition, in the following description, the components composed of polyurethane (A), polyfunctional monomer (B), and other monomers (C) may be referred to as "components (A) ~ (C) )".
<1-1.聚胺基甲酸酯(A)> 聚胺基甲酸酯(A)為具有包含來自聚氧伸烷基多元醇及聚異氰酸酯之結構之骨架的聚胺基甲酸酯。聚胺基甲酸酯(A)包含後述的聚胺基甲酸酯(a1)。為了調節黏著劑組成物之硬化物之凝聚力,聚胺基甲酸酯(A)也可進一步包含後述的聚胺基甲酸酯(a2)。<1-1. Polyurethane (A)> Polyurethane (A) is a polyurethane having a skeleton containing a structure derived from polyoxyalkylene polyol and polyisocyanate. The polyurethane (A) includes the polyurethane (a1) described later. In order to adjust the cohesive force of the cured product of the adhesive composition, the polyurethane (A) may further include the polyurethane (a2) described later.
[聚胺基甲酸酯(a1)] 聚胺基甲酸酯(a1)為具有包含來自聚氧伸烷基多元醇之結構及來自聚異氰酸酯之結構的骨架,且複數之末端具有(甲基)丙烯醯基的聚胺基甲酸酯。又,聚胺基甲酸酯(a1)之末端的(甲基)丙烯醯基,較佳為(甲基)丙烯醯氧基之一部分。[Polyurethane (a1)] Polyurethane (a1) is a polyurethane having a skeleton including a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate, and a plurality of ends having a (meth)acrylic acid group . Furthermore, the (meth)acryloyl group at the terminal of the polyurethane (a1) is preferably a part of the (meth)acryloyloxy group.
[聚胺基甲酸酯(a2)] 聚胺基甲酸酯(a2)為具有包含來自聚氧伸烷基多元醇及聚異氰酸酯之結構的骨架,且僅1個末端具有(甲基)丙烯醯基的聚胺基甲酸酯。又,聚胺基甲酸酯(a2)之末端的(甲基)丙烯醯基,較佳為(甲基)丙烯醯氧基之一部分。 又,聚胺基甲酸酯(A)所含有之聚胺基甲酸酯(a1)與聚胺基甲酸酯(a2)之含量、亦即、聚胺基甲酸酯(A)所含有之聚胺基甲酸酯之末端之(甲基)丙烯醯基之數的調節方法係在聚胺基甲酸酯(A)之製造方法項中,其一例子如後述。[Polyurethane (a2)] The polyurethane (a2) is a polyurethane having a skeleton containing a structure derived from a polyoxyalkylene polyol and a polyisocyanate, and having a (meth)acryloyl group at only one end. Moreover, the (meth)acryloyl group at the terminal of the polyurethane (a2) is preferably a part of the (meth)acryloyloxy group. In addition, the content of polyurethane (a1) and polyurethane (a2) contained in polyurethane (A), that is, the content of polyurethane (A) The method of adjusting the number of (meth)acrylic groups at the end of the polyurethane is in the section of the method for producing polyurethane (A), and an example is described later.
本發明之「複數之末端」,當直鏈聚合物時為2個末端,分枝聚合物時,與各支鏈之支數相同數的末端中,為2個以上的末端。 聚胺基甲酸酯(A)中,不包含聚胺基甲酸酯(a1)、聚胺基甲酸酯(a2)以外的成分。The "plural ends" in the present invention means two ends in the case of a linear polymer, and in the case of a branched polymer, there are two or more ends in the same number of branches as each branch. Polyurethane (A) does not contain components other than polyurethane (a1) and polyurethane (a2).
聚胺基甲酸酯(A)所含有之聚胺基甲酸酯(a1)係以數基準,較佳為聚胺基甲酸酯(A)之80~100%,更佳為90~100%,又更佳為100%。聚胺基甲酸酯(A)所含有之聚胺基甲酸酯(a2)係以數基準,較佳為聚胺基甲酸酯(A)之0~20%,更佳為0~10%,又更佳為0%。聚胺基甲酸酯(A)所含有之聚胺基甲酸酯(a1)為80%以上時,黏著劑組成物之硬化物的凝聚力變得充分大。The polyurethane (a1) contained in the polyurethane (A) is based on the number, preferably 80-100% of the polyurethane (A), more preferably 90-100 %, more preferably 100%. The polyurethane (a2) contained in the polyurethane (A) is on a numerical basis, preferably 0-20% of the polyurethane (A), more preferably 0-10 %, more preferably 0%. When the polyurethane (a1) contained in the polyurethane (A) is 80% or more, the cohesive force of the cured product of the adhesive composition becomes sufficiently large.
「聚氧伸烷基多元醇」 聚氧伸烷基多元醇,較佳為具有碳數2~4之伸烷基鏈者,該具體例,可列舉例如聚氧伸乙基多元醇、聚氧伸丙基多元醇、聚氧伸丁基多元醇等。又,聚氧伸烷基多元醇之中,較佳為使用聚氧烷二醇,特佳為使用聚丙二醇。"Polyoxyalkylene polyol" The polyoxyalkylene polyol is preferably one having an alkylene chain with a carbon number of 2 to 4. The specific examples include polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene Butyl polyol and so on. Moreover, among polyoxyalkylene polyols, it is preferable to use polyoxyalkylene glycol, and it is especially preferable to use polypropylene glycol.
又,作為聚氧伸烷基多元醇,也可含有2種以上之伸烷基鏈。又,作為聚胺基甲酸酯(A),來自2種以上之不同聚氧伸烷基多元醇的結構可為挾著聚異氰酸酯所鍵結的構成。In addition, as the polyoxyalkylene polyol, two or more kinds of alkylene chains may be contained. In addition, as the polyurethane (A), the structure derived from two or more different polyoxyalkylene polyols may be a structure in which polyisocyanate is interposed and bonded.
聚氧伸烷基多元醇之數平均分子量,較佳為500~5,000,更佳為800~4,000,又更佳為1,000~3,000。數平均分子量為500以上時,使黏著劑組成物硬化所得之黏著劑層之剝離強度提高。數平均分子量為5,000以下時,聚胺基甲酸酯中,因包含充分量的胺基甲酸酯鍵,故黏著劑層之凝聚力提高。The number average molecular weight of the polyoxyalkylene polyol is preferably 500 to 5,000, more preferably 800 to 4,000, and still more preferably 1,000 to 3,000. When the number average molecular weight is 500 or more, the peel strength of the adhesive layer obtained by curing the adhesive composition is improved. When the number average molecular weight is 5,000 or less, since a sufficient amount of urethane bonds are contained in the polyurethane, the cohesive force of the adhesive layer increases.
聚氧伸烷基多元醇係較佳為在末端具有2個或3個羥基(二醇或三醇型聚氧伸烷基多元醇)。例如,二醇型的聚丙二醇時,羥基價較佳為20~120mgKOH/g,更佳為30~100mgKOH/g,又更佳為40~80mgKOH/g。聚丙二醇之具體例,可列舉羥基價為56mgKOH/g,在末端具有羥基(hydroxy)之聚丙二醇之ACTCOL D-2000(三井化學製,數平均分子量2000、二醇型)。 在此,羥基價係指依據JISK0070測量之聚氧伸烷基多元醇的羥基價,將該聚氧伸烷基多元醇1g進行乙醯基化時之游離乙酸,進行中和所需的氫氧化鉀之mg數。具體而言,使用乙酸酐,使試料中之羥基乙醯基化,此時所產生之游離乙酸藉由氫氧化鉀溶液滴定,可求得。The polyoxyalkylene polyol preferably has 2 or 3 hydroxyl groups at the terminal (diol or triol type polyoxyalkylene polyol). For example, in the case of glycol type polypropylene glycol, the hydroxyl value is preferably 20 to 120 mgKOH/g, more preferably 30 to 100 mgKOH/g, and still more preferably 40 to 80 mgKOH/g. Specific examples of polypropylene glycol include ACTCOL D-2000 (manufactured by Mitsui Chemicals, number average molecular weight 2000, glycol type) of polypropylene glycol having a hydroxyl value of 56 mgKOH/g and a hydroxy group at the end. Here, the hydroxyl value refers to the hydroxyl value of the polyoxyalkylene polyol measured in accordance with JISK0070. When 1 g of the polyoxyalkylene polyol is acetylated, the free acetic acid is used to neutralize the required hydroxide The mg of potassium. Specifically, acetic anhydride is used to acetylate the hydroxyl group in the sample, and the free acetic acid produced at this time can be obtained by titration with potassium hydroxide solution.
「聚異氰酸酯」 作為聚異氰酸酯,只要是具有複數異氰酸酯基之化合物時,即無特別限定,較佳為二異氰酸酯。二異氰酸酯,可列舉例如甲伸苯基(tolylene)二異氰酸酯及其氫化物、亞二甲苯基二異氰酸酯及其氫化物、二苯基甲烷二異氰酸酯及其氫化物、1,5‐伸萘基二異氰酸酯及其氫化物、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、四甲基亞二甲苯基二異氰酸酯、異佛爾酮 二異氰酸酯、4,4’‐二環己基二異氰酸酯、1,3‐雙(異氰酸酯甲基)環己烷、降莰烷二異氰酸酯等。"Polyisocyanate" The polyisocyanate is not particularly limited as long as it is a compound having a plurality of isocyanate groups, but a diisocyanate is preferred. Examples of diisocyanates include tolylene diisocyanate and its hydrogenated products, xylylene diisocyanate and its hydrogenated products, diphenylmethane diisocyanate and its hydrogenated products, 1,5-naphthylene diisocyanate and its hydrogenated products. Isocyanates and their hydrides, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyl diisocyanate , 1,3-bis(isocyanate methyl)cyclohexane, norbornane diisocyanate, etc.
此等例示之化合物之中,就耐光性、反應性之控制的觀點,較佳為異佛爾酮 二異氰酸酯或二苯基甲烷二異氰酸酯之氫化物,就反應性的觀點,更佳為二苯基甲烷二異氰酸酯之氫化物。聚胺基甲酸酯(A)所含有之來自聚異氰酸酯的結構可為1種類所成者,也可為包含2種類以上的結構。 聚異氰酸酯之具體例,可列舉二苯基甲烷二異氰酸酯之氫化物(DesmodurW、Sumika Covestro Urethane製)、異佛爾酮二異氰酸酯(DesmodurI、Sumika Covestro Urethane製)等。Among these exemplified compounds, from the viewpoint of light resistance and reactivity control, isophorone diisocyanate or diphenylmethane diisocyanate hydride is preferred, and from the viewpoint of reactivity, diphenyl is more preferred Hydrogenated methane diisocyanate. The polyisocyanate-derived structure contained in the polyurethane (A) may be one type, or may include two or more types. Specific examples of the polyisocyanate include hydrogenated diphenylmethane diisocyanate (manufactured by Desmodur W, Sumika Covestro Urethane), isophorone diisocyanate (manufactured by Desmodur I, Sumika Covestro Urethane), and the like.
聚胺基甲酸酯(A)之重量平均分子量為30,000 ~200,000,較佳為50,000~150,000,又更佳為70,000~100,000。聚胺基甲酸酯(A)之重量平均分子量未達30,000時,使黏著劑組成物硬化所得之黏著劑層,其柔軟性不充分,含有此黏著劑層之表面保護薄片不易積層。又,聚胺基甲酸酯(A)之重量平均分子量大於200,000時,作為黏著劑組成物,黏度變高等操作困難,作業性降低。The weight average molecular weight of the polyurethane (A) is 30,000 to 200,000, preferably 50,000 to 150,000, and more preferably 70,000 to 100,000. When the weight average molecular weight of the polyurethane (A) is less than 30,000, the adhesive layer obtained by curing the adhesive composition has insufficient flexibility, and the surface protection sheet containing the adhesive layer is not easy to be laminated. In addition, when the weight average molecular weight of the polyurethane (A) is greater than 200,000, the adhesive composition becomes difficult to handle, such as increased viscosity, and workability decreases.
相對於成分(A)~(C)之合計量,聚胺基甲酸酯(A)之含量為30~60質量%,較佳為35~55質量%,更佳為40~50質量%。聚胺基甲酸酯(A)之含量未達30質量%時,黏著劑組成物之硬化物的凝聚力不足,黏著劑層變得過柔軟,有對黏著面(黏著劑層與被黏物之間)發生挾氣泡的疑慮。聚胺基甲酸酯(A)之含量大於60質量%時,黏著劑組成物之硬化物的凝聚力過高,黏著劑層之柔軟性不足,有黏著劑層對被黏物之潤濕性降低的疑慮。The content of the polyurethane (A) is 30-60% by mass, preferably 35-55% by mass, and more preferably 40-50% by mass relative to the total amount of components (A) to (C). When the content of polyurethane (A) is less than 30% by mass, the cohesive force of the hardened material of the adhesive composition is insufficient, the adhesive layer becomes too soft, and the adhesive surface (between the adhesive layer and the adherend) Intermittently) There is a doubt about air bubbles. When the content of polyurethane (A) is greater than 60% by mass, the cohesive force of the hardened material of the adhesive composition is too high, the flexibility of the adhesive layer is insufficient, and the wettability of the adhesive layer to the adherend decreases Doubts.
<1-2.多官能單體(B)> 多官能單體(B)係調整使用黏著劑組成物之硬化物之黏著劑層(表面保護薄片)的剝離強度。多官能單體(B)係聚胺基甲酸酯(A)除外,具有複數(甲基)丙烯醯基的化合物。(甲基)丙烯醯基之數為2個以上時,無特別限制,就硬化性的觀點,多官能單體(B)為具有3個以上之(甲基)丙烯醯基較佳。<1-2. Multifunctional monomer (B)> The polyfunctional monomer (B) adjusts the peel strength of the adhesive layer (surface protection sheet) of the hardened product of the adhesive composition. The polyfunctional monomer (B) is a compound having a plurality of (meth)acrylic groups except for the polyurethane (A). When the number of (meth)acryloyl groups is 2 or more, it is not particularly limited. From the viewpoint of curability, the polyfunctional monomer (B) preferably has 3 or more (meth)acryloyl groups.
多官能單體(B),較佳為多元醇化合物之聚(甲基)丙烯酸酯,可列舉例如聚乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、羥基新戊酸酯新戊二醇二(甲基)丙烯酸酯、1,3‐雙(羥基乙基)‐5,5‐二甲基乙內醯脲二(甲基)丙烯酸酯、α,ω‐二(甲基)丙烯醯基雙二乙二醇苯二甲酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、1,4‐丁二醇二(甲基)丙烯酸酯、1,6‐己二醇二(甲基)丙烯酸酯、二丙烯醯氧基乙基磷酸酯、二季戊四醇三羥基(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯等。The multifunctional monomer (B) is preferably a poly(meth)acrylate of a polyol compound, for example, polyethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate , 1,3-bis(hydroxyethyl)-5,5-dimethylhydantoin di(meth)acrylate, α,ω-bis(meth)acryloyl bis-diethylene glycol benzene two Formate, trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylic acid Esters, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, dipropylene oxyethyl phosphate, dipentaerythritol trihydroxy(methyl) Acrylate, pentaerythritol tetra(meth)acrylate, etc.
此等之中,就使用黏著劑組成物之表面保護薄片之剝離強度容易壓低調整的觀點,更佳為1,6‐己二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇三羥基(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯,又更佳為三羥甲基丙烷三(甲基)丙烯酸酯。又,多官能單體(B)可為由1種類的化合物所成者,有可為由2種類以上之化合物所成者。Among these, from the viewpoint that the peel strength of the surface protection sheet using the adhesive composition is easy to be reduced and adjusted, it is more preferably 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(methyl) Yl)acrylate, dipentaerythritol trihydroxy(meth)acrylate, pentaerythritol tetra(meth)acrylate, and more preferably trimethylolpropane tri(meth)acrylate. In addition, the polyfunctional monomer (B) may be composed of one type of compound, or may be composed of two or more types of compounds.
相對於成分(A)~(C)之合計量,多官能單體(B)之含量為2~10質量%,較佳為3~9質量%,更佳為4~8質量%。含量為未達2質量%時,表面保護薄片之剝離強度過高,輕剝離性差。含量多於10質量%時,使用黏著劑組成物之硬化物的黏著劑層變硬,薄片之切斷加工時,變得容易發生龜裂。又,含量多於10質量%時,作為表面保護薄片,有霧度變高的傾向。The content of the polyfunctional monomer (B) is 2-10% by mass, preferably 3-9% by mass, more preferably 4-8% by mass relative to the total amount of components (A) to (C). When the content is less than 2% by mass, the peel strength of the surface protection sheet is too high and the light peelability is poor. When the content is more than 10% by mass, the adhesive layer of the hardened product using the adhesive composition becomes hard, and cracks are likely to occur when the sheet is cut. Moreover, when the content is more than 10% by mass, the haze tends to increase as a surface protection sheet.
<1-3.其他的單體(C)> 其他的單體(C)係聚胺基甲酸酯(A)除外,且多官能單體(B)除外的化合物,可與聚胺基甲酸酯(A)及多官能單體(B)聚合時,即無特別限定。但是其他的單體(C)係作為與聚胺基甲酸酯(A)及多官能單體(B)聚合用的官能基,較佳為具有可自由基聚合之乙烯性不飽和鍵,其中,更佳為具有乙烯基或(甲基)丙烯醯基,又更佳為具有(甲基)丙烯醯基者。<1-3. Other monomers (C)> Other monomers (C) are excluding polyurethane (A), and compounds other than polyfunctional monomer (B) can be combined with polyurethane (A) and polyfunctional monomer (B) At the time of polymerization, there is no particular limitation. However, other monomers (C) are used as functional groups for polymerization with polyurethane (A) and polyfunctional monomers (B), and preferably have a radically polymerizable ethylenic unsaturated bond. , More preferably having a vinyl group or (meth)acrylic acid group, and still more preferably having a (meth)acrylic acid group.
其他的單體(C),無特別限定,可列舉烷基(甲基)丙烯酸酯、環狀烷基(甲基)丙烯酸酯、烷氧基烷基(甲基)丙烯酸酯、烷氧基(聚)伸烷二醇(甲基)丙烯酸酯、含有羥基之(甲基)丙烯酸酯、含有羧基之(甲基)丙烯酸酯、氟化烷基(甲基)丙烯酸酯、二烷基胺基烷基(甲基)丙烯酸酯、(甲基)丙烯醯胺、含有環氧基之(甲基)丙烯酸酯、不飽和羧酸等。Other monomers (C) are not particularly limited, and examples include alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, and alkoxy ( Poly)alkylene glycol (meth)acrylate, hydroxyl-containing (meth)acrylate, carboxyl-containing (meth)acrylate, fluorinated alkyl (meth)acrylate, dialkylamino alkane (Meth)acrylate, (meth)acrylamide, epoxy-containing (meth)acrylate, unsaturated carboxylic acid, etc.
烷基(甲基)丙烯酸酯,可列舉例如甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、n‐丙基(甲基)丙烯酸酯、n‐丁基(甲基)丙烯酸酯、tert‐丁基(甲基)丙烯酸酯、異丁基(甲基)丙烯酸酯、2‐乙基己基(甲基)丙烯酸酯、異癸基(甲基)丙烯酸酯、n‐己基(甲基)丙烯酸酯、異辛基(甲基)丙烯酸酯、異十八烷基(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、十三烷基(甲基)丙烯酸酯等。Alkyl (meth)acrylates, for example, meth (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylic acid Ester, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-hexyl (meth)acrylate, Yl)acrylate, isooctyl (meth)acrylate, isooctadecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, etc.
環狀烷基(甲基)丙烯酸酯,可列舉例如環己基(甲基)丙烯酸酯、降莰基(甲基)丙烯酸酯、異莰基(甲基)丙烯酸酯、降茨烷基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、二環戊烯氧基乙基(甲基)丙烯酸酯、二環戊基(甲基)丙烯酸酯、二環戊氧基乙基(甲基)丙烯酸酯等。Cyclic alkyl (meth)acrylates include, for example, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate. )Acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentyloxyethyl ( Meth) acrylate and the like.
烷氧基烷基(甲基)丙烯酸酯,可列舉例如乙氧基乙基(甲基)丙烯酸酯、甲氧基乙基(甲基)丙烯酸酯、丁氧基乙基(甲基)丙烯酸酯、2‐甲氧基乙氧基乙基(甲基)丙烯酸酯、2‐乙氧基乙氧基乙基(甲基)丙烯酸酯等。Alkoxyalkyl (meth)acrylates include, for example, ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate , 2-Methoxyethoxyethyl (meth)acrylate, 2-ethoxyethoxyethyl (meth)acrylate, etc.
烷氧基(聚)伸烷二醇(甲基)丙烯酸酯,可列舉例如甲氧基二乙二醇(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯等。Alkoxy (poly)alkylene glycol (meth)acrylate, for example, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxy Dipropylene glycol (meth)acrylate and the like.
含有羥基之(甲基)丙烯酸酯,可列舉例如2‐羥基乙基(甲基)丙烯酸酯、2‐羥基丙基(甲基)丙烯酸酯、4‐羥基丁基(甲基)丙烯酸酯、1,3‐丁二醇單(甲基)丙烯酸酯、1,4‐丁二醇單(甲基)丙烯酸酯、1,6‐己二醇單(甲基)丙烯酸酯、3‐甲基戊二醇單(甲基)丙烯酸酯等。Hydroxy-containing (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1 , 3-butanediol mono(meth)acrylate, 1,4-butanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, 3-methylpentadiene Alcohol mono(meth)acrylate etc.
含有羧基之(甲基)丙烯酸酯,可列舉例如β‐羧基乙基(甲基)丙烯酸酯等。Examples of the (meth)acrylate containing a carboxyl group include β-carboxyethyl (meth)acrylate.
氟化烷基(甲基)丙烯酸酯,可列舉例如八氟戊基(甲基)丙烯酸酯等。Examples of the fluorinated alkyl (meth)acrylate include octafluoropentyl (meth)acrylate.
二烷基胺基烷基(甲基)丙烯酸酯,可列舉例如N,N‐二甲基胺基乙基(甲基)丙烯酸酯、N,N‐二乙基胺基乙基(甲基)丙烯酸酯等。Dialkylaminoalkyl (meth)acrylates, for example, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth) Acrylic etc.
(甲基)丙烯醯胺,可列舉例如(甲基)丙烯醯胺、N‐甲基(甲基)丙烯醯胺、N‐乙基(甲基)丙烯醯胺、N‐丙基(甲基)丙烯醯胺、N‐異丙基丙烯醯胺、N‐己基(甲基)丙烯醯胺、N,N‐二甲基(甲基)丙烯醯胺、N,N‐二乙基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉、二丙酮丙烯醯胺等。(Meth)acrylamide, for example (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(methyl) )Acrylamide, N-isopropylacrylamide, N-hexyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(methyl) ) Acrylamide, (meth)acrylamide morpholine, diacetone acrylamide, etc.
含有環氧基之(甲基)丙烯酸酯,可列舉例如縮水甘油基(甲基)丙烯酸酯等。 不飽和羧酸,可列舉(甲基)丙烯酸、馬來酸、依康酸等。The epoxy group-containing (meth)acrylate includes, for example, glycidyl (meth)acrylate. Examples of unsaturated carboxylic acids include (meth)acrylic acid, maleic acid, and itaconic acid.
又,其他的單體(C),上述化合物除外,可列舉例如丙烯腈、甲基丙烯腈、苯乙烯、α‐甲基苯乙烯、乙酸乙烯酯、丙酸乙烯酯、硬脂酸乙烯酯、氯乙烯、偏二氯乙烯、烷基乙烯醚、乙烯基甲苯、N‐乙烯基吡啶、N‐乙烯基吡咯烷酮、依康酸二烷基酯、富馬酸二烷基酯、烯丙基醇、羥基丁基乙烯醚、羥基乙基乙烯醚、4‐羥基甲基環己基甲基乙烯醚、三乙二醇單乙烯醚或二乙二醇單乙烯醚、甲基乙烯基酮、N‐丙烯醯胺甲基三甲基氯化銨、烯丙基三甲基氯化銨、二甲基烯丙基乙烯基酮等。In addition, other monomers (C), excluding the above-mentioned compounds, include, for example, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, Vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, N-vinylpyridine, N-vinylpyrrolidone, dialkyl itconate, dialkyl fumarate, allyl alcohol, Hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, 4-hydroxymethyl cyclohexyl methyl vinyl ether, triethylene glycol monovinyl ether or diethylene glycol monovinyl ether, methyl vinyl ketone, N-acrylic acid Aminomethyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride, dimethyl allyl vinyl ketone, etc.
此等例示之化合物之中,就與聚胺基甲酸酯(A)的相溶性、黏著劑組成物的黏度、剝離強度之調整的觀點,較佳為烷基(甲基)丙烯酸酯,更佳為2‐乙基己基(甲基)丙烯酸酯、異辛基(甲基)丙烯酸酯、異十八烷基(甲基)丙烯酸酯、異莰基(甲基)丙烯酸酯,又更佳為2‐乙基己基(甲基)丙烯酸酯。又,其他的單體(C),可為由1種類之化合物所成者,也可為由2種類以上之化合物所成者。Among these exemplified compounds, from the viewpoint of the compatibility with the polyurethane (A), the viscosity of the adhesive composition, and the adjustment of the peel strength, the alkyl (meth)acrylate is more preferred, and Preferably it is 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isooctadecyl (meth)acrylate, isobornyl (meth)acrylate, and more preferably 2-Ethylhexyl (meth)acrylate. In addition, the other monomer (C) may be composed of one type of compound or may be composed of two or more types of compounds.
相對於成分(A)~(C)之合計量,其他的單體(C)之含量為30~68質量%,較佳為35~62質量%,更佳為40~56質量%。含量為未達30質量%時,黏著劑組成物之硬化物的凝聚力過高,黏著劑層之柔軟性不足,對被黏物之潤濕性有降低的疑慮。含量為高於68質量%時,黏著劑組成物之硬化物的凝聚力變小,黏著劑層過柔軟,對黏著面(黏著劑層與被黏物之間)有發生挾氣泡的疑慮。The content of other monomers (C) is 30 to 68% by mass, preferably 35 to 62% by mass, and more preferably 40 to 56% by mass relative to the total amount of components (A) to (C). When the content is less than 30% by mass, the cohesive force of the hardened material of the adhesive composition is too high, the flexibility of the adhesive layer is insufficient, and there is a concern about the wettability of the adherend. When the content is higher than 68% by mass, the cohesive force of the hardened material of the adhesive composition becomes small, the adhesive layer is too soft, and there is a concern that air bubbles may occur on the adhesive surface (between the adhesive layer and the adherend).
<1-4.光聚合起始劑(D)> 光聚合起始劑(D),無特別限定,可列舉羰基系光聚合起始劑、硫系光聚合起始劑、醯基氧化磷系光聚合起始劑、醌系光聚合起始劑、磺醯氯( sulfonyl chloride)系光聚合起始劑、噻噸酮系光聚合起始劑等。<1-4. Photopolymerization initiator (D)> The photopolymerization initiator (D) is not particularly limited, and examples include carbonyl-based photopolymerization initiators, sulfur-based photopolymerization initiators, oxyphosphorus-based photopolymerization initiators, quinone-based photopolymerization initiators, Sulfonyl chloride (sulfonyl chloride)-based photopolymerization initiator, thioxanthone-based photopolymerization initiator, etc.
羰基系光聚合起始劑,可列舉例如二苯甲酮、二苯基乙二酮、苯偶因、ω‐溴苯乙酮、氯丙酮、苯乙酮、2,2‐二乙氧基苯乙酮、2,2‐二甲氧基‐2‐苯基苯乙酮、p‐二甲基胺基苯乙酮、p‐二甲基胺基苯丙酮、2‐氯二苯甲酮、4,4’‐二氯二苯甲酮、4,4’‐雙二乙基胺基二苯甲酮、米希勒酮、苯偶因甲醚、苯偶因異丁醚、苯偶因‐n‐丁醚、苄基甲基縮醛、1‐羥基環己基苯基酮、2‐羥基‐2‐甲基‐1‐苯基‐丙烷‐1‐酮、1‐(4‐異丙基苯基)‐2‐羥基‐2‐甲基丙烷‐1‐酮、甲基苯甲醯基甲酸酯、2,2‐二乙氧基苯乙酮、4‐N,N’‐二甲基苯乙酮、2‐甲基‐1‐[4‐(甲硫基)苯基]‐2‐嗎啉基丙烷‐1‐酮等。Carbonyl-based photopolymerization initiators include, for example, benzophenone, diphenylethylenedione, benzidine, ω-bromoacetophenone, chloroacetone, acetophenone, and 2,2-diethoxybenzene Ethyl ketone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, 4 ,4'-Dichlorobenzophenone, 4,4'-Diethylaminobenzophenone, Michlerone, Benzene methyl ether, Benzene isobutyl ether, Benzene-n -Butyl ether, benzyl methyl acetal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropylphenyl) )-2-Hydroxy-2-methylpropane-1-ketone, methylbenzyl formate, 2,2-diethoxyacetophenone, 4-N,N'-dimethyl styrene Ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, etc.
硫系光聚合起始劑,可列舉例如二苯基二硫醚、聯苄二硫醚、四乙基秋蘭姆二硫化物、四甲銨單硫化物等。Examples of the sulfur-based photopolymerization initiator include diphenyl disulfide, bibenzyl disulfide, tetraethylthiuram disulfide, and tetramethylammonium monosulfide.
醯基氧化膦( phosphine oxide) 系光聚合起始劑,可列舉例如2,4,6‐三甲基苯甲醯基二苯基氧化膦、2,4,6‐三甲基苯甲醯基苯基乙氧基氧化膦等。Phosphine oxide ( phosphine oxide ) is a photopolymerization initiator, for example 2,4,6-trimethylbenzyl diphenyl phosphine oxide, 2,4,6-trimethylbenzyl Phenyl ethoxy phosphine oxide and so on.
醌系光聚合起始劑,可列舉例如苯醌、蒽醌等之醌系光聚合起始劑。Examples of the quinone-based photopolymerization initiator include quinone-based photopolymerization initiators such as benzoquinone and anthraquinone.
磺醯氯(sulfonyl chloride)系光聚合起始劑,可列舉例如2‐萘磺醯氯等。Sulfonyl chloride (sulfonyl chloride)-based photopolymerization initiators include, for example, 2-naphthalenesulfonyl chloride.
噻噸酮系光聚合起始劑,可列舉例如噻噸酮、2‐氯噻噸酮、2‐甲硫基呫噸酮等。The thioxanthone-based photopolymerization initiator includes, for example, thioxanthone, 2-chlorothiaxanthone, 2-methylthioxanthone, and the like.
此等例示之化合物之中,就使黏著劑組成物硬化所得之黏著劑層之透明性的觀點,較佳為1‐羥基環己基苯基酮、2,4,6‐三甲基苯甲醯基二苯基氧化膦。又,光聚合起始劑(D),可為由1種類之化合物所成者,也可為由2種類以上之化合物所成者。Among these exemplified compounds, from the viewpoint of the transparency of the adhesive layer obtained by curing the adhesive composition, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzyl are preferred Diphenyl phosphine oxide. In addition, the photopolymerization initiator (D) may be composed of one type of compound, or may be composed of two or more types of compounds.
相對於成分(A)~(C)之合計量100質量份,光聚合起始劑(D)之含量為0.1~5質量份,較佳為0.2~3質量份,更佳為0.3~2質量份。光聚合起始劑(D)之含量未達0.1質量份時,黏著劑組成物未充分地進行光硬化,大於5質量份時,生成許多低分子量成分,所得之表面保護薄片之剝離性產生惡化的傾向。The content of the photopolymerization initiator (D) is 0.1 to 5 parts by mass, preferably 0.2 to 3 parts by mass, more preferably 0.3 to 2 parts by mass relative to 100 parts by mass of the total amount of components (A) to (C) Copies. When the content of the photopolymerization initiator (D) is less than 0.1 parts by mass, the adhesive composition is not sufficiently photocured, and when it is greater than 5 parts by mass, many low molecular weight components are formed, and the peelability of the resulting surface protection sheet deteriorates Propensity.
<1-5.添加劑> 黏著劑組成物中,為了提高所得之表面保護薄片之積層性(潤濕性)、除泡性(貼合時所挾著之氣泡去除容易度),必要時,可添加脂肪酸酯。脂肪酸酯之例,可列舉碳數為8~18之一元酸、或多元酸與碳數為18以下之分枝醇之酯、碳數為14~18之不飽和脂肪酸、或具有支鏈之酸與4價醇之酯等。脂肪酸酯較佳之具體例,可列舉肉豆蔻酸異丙酯。相對於成分(A)~(C)之合計量100質量份,脂肪酸酯之添加量,較佳為1~40質量份,更佳為3~35質量份,又更佳為5~30質量份。<1-5. Additives> In the adhesive composition, in order to improve the layering properties (wettability) and defoaming properties (easy to remove bubbles entrapped during bonding) of the obtained surface protection sheet, fatty acid esters may be added if necessary. Examples of fatty acid esters include monobasic acids with 8 to 18 carbons, or esters of polybasic acids and branch alcohols with carbons of 18 or less, unsaturated fatty acids with 14 to 18 carbons, or branched Esters of acids and tetravalent alcohols, etc. Preferred specific examples of fatty acid esters include isopropyl myristate. Relative to 100 parts by mass of the total amount of components (A) to (C), the amount of fatty acid ester added is preferably 1-40 parts by mass, more preferably 3~35 parts by mass, and still more preferably 5-30 parts by mass Copies.
又,黏著劑組成物中,在不損及透明性的範圍內,必要時可添加其他的添加劑。添加劑可列舉例如可塑劑、表面潤滑劑、平坦劑、軟化劑、抗氧化劑、防老化劑、光安定劑、紫外線吸收劑、聚合抑制劑、苯并***系等之光安定劑、磷酸酯系及其他的難燃劑、如界面活性劑之抗靜電劑、染料等。In addition, in the adhesive composition, other additives may be added as necessary within a range that does not impair transparency. Additives include, for example, plasticizers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, benzotriazole-based light stabilizers, phosphate ester-based And other flame retardants, such as surfactants, antistatic agents, dyes, etc.
<1-6.溶劑> 黏著劑組成物係因含有作為低分子量成分之多官能單體(B)、其他的單體(C),故即使未添加溶劑,也可調整成為可塗佈的黏度。亦即,黏著劑組成物除了由前述聚胺基甲酸酯(A)、前述多官能單體(B)、前述其他的單體(C)及光聚合起始劑(D)所成之必須成分外,實質上可不含溶劑。此時,製造表面保護薄片時,可省略將溶劑加熱乾燥的步驟,生產性升高。特別是製造超過50μm之膜厚的表面保護薄片時,黏著劑組成物實質上不含該溶劑較佳。本發明之「實質上不含」的意思係本發明之黏著劑組成物中之前述溶劑的含量為0~1質量%,較佳為0~0.5質量%,更佳為0~0.1質量%。 黏著劑組成物為了塗佈時之黏度調整,也可添加溶劑。溶劑係因黏著劑組成物所含有之其他的成分等可適宜選擇,較佳為有機溶劑。 可使用的有機溶劑,無特別限定,可列舉甲基乙基酮、丙酮、乙酸乙酯、四氫呋喃、二噁烷、環己酮、n‐己烷、甲苯、二甲苯、n‐丙醇、異丙醇等。此等有機溶劑可單獨使用,也可混合2種以上使用。溶劑係將黏著劑組成物塗佈於基材等後,藉由乾燥除去後,進行光硬化較佳。<1-6. Solvent> Since the adhesive composition contains a polyfunctional monomer (B) as a low molecular weight component and other monomers (C), even if a solvent is not added, the viscosity can be adjusted to be coatable. That is, the adhesive composition is in addition to the aforementioned polyurethane (A), the aforementioned multifunctional monomer (B), the aforementioned other monomers (C) and the photopolymerization initiator (D). Except for the ingredients, it may be substantially free of solvent. In this case, when manufacturing the surface protection sheet, the step of heating and drying the solvent can be omitted, and the productivity is improved. In particular, when manufacturing a surface protection sheet having a film thickness of more than 50 μm, it is preferable that the adhesive composition does not substantially contain the solvent. The meaning of "substantially free" in the present invention means that the content of the aforementioned solvent in the adhesive composition of the present invention is 0 to 1% by mass, preferably 0 to 0.5% by mass, and more preferably 0 to 0.1% by mass. In order to adjust the viscosity of the adhesive composition during application, a solvent may be added. The solvent can be appropriately selected due to other components contained in the adhesive composition, and an organic solvent is preferred. The usable organic solvent is not particularly limited, and examples include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol, iso Propanol and so on. These organic solvents may be used alone or in combination of two or more kinds. The solvent is preferably used for photo-curing after coating the adhesive composition on a substrate or the like and then removing it by drying.
<2.表面保護薄片用黏著劑組成物之製造方法> 又,在此,說明聚胺基甲酸酯(A)之合成方法之例子,但是多官能單體(B)及其他的單體(C)及表面保護薄片用黏著劑組成物所含有之其他成分,市售品之購入容易,且因使用之化合物的種類,有各種的合成方法,故省略合成方法之說明。<2. Manufacturing method of adhesive composition for surface protection sheet> Also, here, an example of the synthesis method of polyurethane (A) is explained, but the polyfunctional monomer (B) and other monomers (C) and others contained in the adhesive composition for surface protection sheets The ingredients and commercial products are easy to purchase, and there are various synthesis methods depending on the type of compound used, so the description of the synthesis method is omitted.
<2-1.聚胺基甲酸酯(A)之合成方法> 以下說明本實施形態之黏著劑組成物所含有之聚胺基甲酸酯(A)之較佳合成方法之一例,但是聚胺基甲酸酯(A)之合成方法不限於此,因合成用的原料或設備等的條件可適宜變更。又,此例中,羥基與異氰酸酯基之反應,在任一的步驟中,也在對異氰酸酯基惰性的有機溶劑之存在下,使用二丁基錫二月桂酸酯、二丁基錫二乙基己酸酯、二辛基錫二月桂酸酯等之胺基甲酸酯化觸媒進行反應。反應係在30~100℃下繼續進行1~5小時為佳。胺基甲酸酯化觸媒之使用量係相對於反應物的總質量,較佳為50~500質量ppm。<2-1. Synthesis method of polyurethane (A)> The following describes an example of a preferable synthesis method of polyurethane (A) contained in the adhesive composition of this embodiment, but the synthesis method of polyurethane (A) is not limited to this, because it is used for synthesis The conditions of raw materials or equipment can be changed as appropriate. Also, in this example, the reaction between the hydroxyl group and the isocyanate group, in any of the steps, is also used in the presence of an organic solvent inert to the isocyanate group, using dibutyltin dilaurate, dibutyltin diethylhexanoate, and Carbamate catalysts such as octyltin dilaurate react. It is better to keep the reaction system at 30~100℃ for 1~5 hours. The usage amount of the urethane catalyst is relative to the total mass of the reactants, and is preferably 50 to 500 mass ppm.
首先,將聚氧伸烷基多元醇與聚異氰酸酯以異氰酸酯基量(數基準,以下相同)多於羥基量(數基準,以下相同)的比例投入,使此等反應,合成在末端具有異氰酸酯基的聚胺基甲酸酯。聚氧伸烷基多元醇及聚異氰酸酯之具體例係如聚胺基甲酸酯(A)項所例示。First, the polyoxyalkylene polyol and the polyisocyanate are charged in a ratio in which the amount of isocyanate groups (on the basis of numbers, the same below) is greater than the amount of hydroxyl groups (on the basis of numbers, the same below), and these are reacted to synthesize having isocyanate groups at the ends. Of polyurethane. Specific examples of polyoxyalkylene polyol and polyisocyanate are as illustrated in the section of polyurethane (A).
此時,藉由調整相對於羥基量之異氰酸酯基量,可調整分子量(聚合度)。具體而言,相對於羥基量之異氰酸酯基量之過剩量越少,具有異氰酸酯基之聚胺基甲酸酯之分子量越大,相對於羥基量之異氰酸酯基量之過剩量越多,具有異氰酸酯基之聚胺基甲酸酯之分子量越小。At this time, by adjusting the amount of isocyanate groups relative to the amount of hydroxyl groups, the molecular weight (degree of polymerization) can be adjusted. Specifically, the smaller the excess amount of isocyanate groups relative to the amount of hydroxyl groups, the greater the molecular weight of the polyurethane having isocyanate groups, and the greater the excess amount of isocyanate groups relative to the amount of hydroxyl groups, the greater the amount of isocyanate groups having isocyanate groups. The smaller the molecular weight of the polyurethane.
其次,使在末端具有異氰酸酯基之聚胺基甲酸酯與具有羥基及(甲基)丙烯醯基的化合物反應,合成在分子鏈末端具有(甲基)丙烯醯基的聚胺基甲酸酯(A)。又,此化合物所含有之(甲基)丙烯醯基,較佳為(甲基)丙烯醯氧基之一部分。Next, a polyurethane having an isocyanate group at the end is reacted with a compound having a hydroxyl group and a (meth)acrylic group to synthesize a polyurethane having a (meth)acrylic group at the end of the molecular chain (A). In addition, the (meth)acryloyl group contained in this compound is preferably a part of the (meth)acryloyloxy group.
具有羥基及(甲基)丙烯醯基的化合物,無特別限定,可列舉2‐羥基乙基(甲基)丙烯酸酯、2‐羥基丙基(甲基)丙烯酸酯、4‐羥基丁基(甲基)丙烯酸酯等之羥基烷基(甲基)丙烯酸酯;1,3‐丁二醇單(甲基)丙烯酸酯、1,4‐丁二醇單(甲基)丙烯酸酯、1,6‐己二醇單(甲基)丙烯酸酯、3‐甲基戊二醇單(甲基)丙烯酸酯等之來自各種多元醇之具有(甲基)丙烯醯基的單醇等。此等可單獨使用,也可組合2種類以上使用。其中,就與異氰酸酯基之反應性、光硬化性的觀點,較佳為2‐羥基乙基(甲基)丙烯酸酯。The compound having a hydroxy group and a (meth)acryloyl group is not particularly limited, and examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Yl) acrylate and other hydroxyalkyl (meth)acrylates; 1,3-butanediol mono(meth)acrylate, 1,4-butanediol mono(meth)acrylate, 1,6- Hexanediol mono(meth)acrylate, 3-methylpentanediol mono(meth)acrylate, etc., are derived from various polyols and have (meth)acrylic acid monools. These can be used alone or in combination of two or more types. Among them, from the viewpoint of reactivity with an isocyanate group and photocurability, 2-hydroxyethyl (meth)acrylate is preferred.
又,除了具有羥基及(甲基)丙烯醯基之化合物,藉由併用不具有(甲基)丙烯醯基,具有1個羥基之烷基醇,與末端具有異氰酸酯基之聚胺基甲酸酯反應,可調整(甲基)丙烯醯基之導入量。烷基醇,無特別限定,可列舉直鏈型、分枝型、脂環型的烷基醇等,此等可單獨使用,也可組合2種類以上使用。藉此,生成在至少任一末端上具有來自上述烷基醇之結構的聚胺基甲酸酯。此時,聚胺基甲酸酯(A)中,包含在至少任一末端不具有(甲基)丙烯醯基的聚胺基甲酸酯。因此,也可包含僅一末端具有(甲基)丙烯醯基的聚胺基甲酸酯(a2)。Also, in addition to the compound having a hydroxyl group and a (meth)acryloyl group, an alkyl alcohol having no (meth)acryloyl group but one hydroxyl group is used in combination with a polyurethane having an isocyanate group at the end In the reaction, the introduction amount of (meth)acryloyl group can be adjusted. The alkyl alcohol is not particularly limited, and examples include linear, branched, and alicyclic alkyl alcohols. These may be used alone or in combination of two or more types. Thereby, a polyurethane having a structure derived from the above-mentioned alkyl alcohol on at least any one end is produced. In this case, the polyurethane (A) includes a polyurethane that does not have a (meth)acryl group at at least any terminal. Therefore, polyurethane (a2) having a (meth)acryloyl group at only one end may be included.
以數基準,在聚胺基甲酸酯(A)所含有之聚胺基甲酸酯之末端之90~100%被導入(甲基)丙烯醯基較佳,更佳為95~100%,又更佳為100%。(甲基)丙烯醯基之導入量為相對於異氰酸酯基,以數基準為90%以上時,可充分得到使黏著劑組成物硬化所得之黏著劑層的凝聚力。相對於全部聚胺基甲酸酯分子鏈之末端數,導入(甲基)丙烯醯基之末端數之比例,可藉由IR、NMR等測量。On a numerical basis, 90-100% of the ends of the polyurethane contained in the polyurethane (A) is preferably introduced with (meth)acrylic groups, more preferably 95-100%, More preferably, it is 100%. When the introduced amount of the (meth)acryloyl group is 90% or more on a numerical basis relative to the isocyanate group, the cohesive force of the adhesive layer obtained by curing the adhesive composition can be sufficiently obtained. The ratio of the number of (meth)acrylic acid groups introduced with respect to the number of ends of the entire polyurethane molecular chain can be measured by IR, NMR, etc.
<2-2.聚胺基甲酸酯(A)之合成方法之變形例> 說明聚胺基甲酸酯(A)之合成方法之變形例。又,此例與上述例同樣,羥基與異氰酸酯基之反應在任一步驟中,在對異氰酸酯基不活性的有機溶劑之存在下,使用二丁基錫二月桂酸酯、二丁基錫二乙基己酸酯、二辛基錫二月桂酸酯等之胺基甲酸酯化觸媒進行反應。反應係在30~100℃下繼續進行1~5小時為佳。胺基甲酸酯化觸媒之使用量係相對於反應物的總質量,較佳為50~500質量ppm。本變形例中,首先,以羥基量多於異氰酸酯基量的比例,使聚氧伸烷基多元醇與聚異氰酸酯反應,合成在末端具有羥基的聚胺基甲酸酯。<2-2. Modification of the synthetic method of polyurethane (A)> A modification example of the synthesis method of polyurethane (A) is explained. In addition, this example is the same as the above example. In any step of the reaction between the hydroxyl group and the isocyanate group, dibutyltin dilaurate, dibutyltin diethylhexanoate, and dibutyltin diethylhexanoate are used in the presence of an organic solvent that is inactive to isocyanate groups. Carbamate catalysts such as dioctyltin dilaurate react. It is better to keep the reaction system at 30~100℃ for 1~5 hours. The usage amount of the urethane catalyst is relative to the total mass of the reactants, and is preferably 50 to 500 mass ppm. In this modification, first, the polyoxyalkylene polyol and the polyisocyanate are reacted at a ratio in which the amount of hydroxyl groups is greater than the amount of isocyanate groups to synthesize a polyurethane having a hydroxyl group at the terminal.
此時,與上述例同樣,藉由調整相對於異氰酸酯基量的羥基量,可調整分子量。具體而言,相對於異氰酸酯基量的羥基量之過剩量越少,具有羥基之聚胺基甲酸酯之分子量越大,相對於異氰酸酯基量的羥基量之過剩量越多,具有羥基之聚胺基甲酸酯之分子量越小。At this time, as in the above example, the molecular weight can be adjusted by adjusting the amount of hydroxyl groups relative to the amount of isocyanate groups. Specifically, the smaller the excess amount of hydroxyl groups relative to the amount of isocyanate groups, the larger the molecular weight of the polyurethane having hydroxyl groups, and the greater the excess amount of hydroxyl groups relative to the amount of isocyanate groups, and the greater the excess amount of hydroxyl groups relative to the amount of isocyanate groups. The smaller the molecular weight of the urethane.
其次,使在末端具有羥基之聚胺基甲酸酯與具有異氰酸酯基及(甲基)丙烯醯基的化合物反應,合成在分子鏈末端具有(甲基)丙烯醯基的聚胺基甲酸酯(A)。又,此化合物所含有之(甲基)丙烯醯基,較佳為(甲基)丙烯醯氧基之一部分。Next, a polyurethane having a hydroxyl group at the end is reacted with a compound having an isocyanate group and a (meth)acrylic group to synthesize a polyurethane having a (meth)acrylic group at the end of the molecular chain (A). In addition, the (meth)acryloyl group contained in this compound is preferably a part of the (meth)acryloyloxy group.
具有異氰酸酯基及(甲基)丙烯醯基之化合物,無特別限定,可列舉2‐(甲基)丙烯醯氧基乙基異氰酸酯、2‐(甲基)丙烯醯氧基丙基異氰酸酯、1,1‐雙(丙烯醯氧基甲基)乙基異氰酸酯等。又,具有異氰酸酯基及(甲基)丙烯醯基之化合物的市售品,可例示例如昭和電工股份公司製之Karenz MOI(註冊商標)或KarenzAOI(註冊商標)等。此等可單獨使用,也可組合2種類以上使用。其中,就與羥基之反應性、光硬化性的觀點,較佳為2‐(甲基)丙烯醯氧基乙基異氰酸酯。The compound having an isocyanate group and a (meth)acryloyl group is not particularly limited, and examples include 2-(meth)acryloyloxyethyl isocyanate, 2-(meth)acryloyloxypropyl isocyanate, 1, 1-bis(acryloxymethyl)ethyl isocyanate and the like. In addition, examples of commercially available products of compounds having isocyanate groups and (meth)acryloyl groups include Karenz MOI (registered trademark) or Karenz AOI (registered trademark) manufactured by Showa Denko Corporation. These can be used alone or in combination of two or more types. Among them, from the viewpoint of reactivity with a hydroxyl group and photocurability, 2-(meth)acryloxyethyl isocyanate is preferred.
又,除了具有異氰酸酯基及(甲基)丙烯醯基之化合物外,藉由併用不具有(甲基)丙烯醯基,具有1個異氰酸酯基之烷基異氰酸酯,與末端具有羥基之聚胺基甲酸酯反應,可調整(甲基)丙烯醯基之導入量。烷基異氰酸酯,無特別限定,可列舉直鏈型、分枝型、脂環型之烷基異氰酸酯等,此等可單獨使用,也可組合2種類以上使用。藉此,生成在至少任一末端具有來自上述烷基異氰酸酯之構造的聚胺基甲酸酯。此時,聚胺基甲酸酯(A)中包含在至少任一末端不具有(甲基)丙烯醯基之聚胺基甲酸酯。因此,此時,聚胺基甲酸酯(A)中也可包含僅1個末端具有(甲基)丙烯醯基的聚胺基甲酸酯。In addition, in addition to compounds having isocyanate groups and (meth)acrylic groups, the combination of alkyl isocyanates that do not have (meth)acrylic groups but one isocyanate group, and polyurethanes having hydroxyl groups at the end The acid ester reaction can adjust the introduction amount of (meth)acryloyl group. The alkyl isocyanate is not particularly limited, and examples include linear, branched, and alicyclic alkyl isocyanates. These may be used alone or in combination of two or more types. As a result, a polyurethane having a structure derived from the above-mentioned alkyl isocyanate at at least any one end is produced. In this case, the polyurethane (A) includes a polyurethane that does not have a (meth)acryloyl group at at least any terminal. Therefore, in this case, the polyurethane (A) may contain a polyurethane having a (meth)acryloyl group at only one terminal.
以數基準,在聚胺基甲酸酯(A)所含有之聚胺基甲酸酯之末端之90~100%導入(甲基)丙烯醯基較佳,更佳為95~100%,又更佳為100%。(甲基)丙烯醯基之導入量為相對於異氰酸酯基,以數基準為90%以上時,可充分得到使黏著劑組成物硬化所得之黏著劑層的凝聚力。On a numerical basis, it is better to introduce (meth)acrylic groups at 90-100% of the ends of the polyurethane contained in the polyurethane (A), and more preferably 95-100%, and More preferably, it is 100%. When the introduced amount of the (meth)acryloyl group is 90% or more on a numerical basis relative to the isocyanate group, the cohesive force of the adhesive layer obtained by curing the adhesive composition can be sufficiently obtained.
<2-3.表面保護薄片用黏著劑組成物所含有之各成分的混合方法> 藉由混合聚胺基甲酸酯(A)、多官能單體(B)、其他的單體(C)、光聚合起始劑(D)、必要時所添加的脂肪酸酯、其他的添加劑、及有機溶劑,製造黏著劑組成物。混合方法,無特別限定,例如可使用均質分散機、裝設槳有翼等之攪拌葉片的攪拌裝置進行。<2-3. How to mix the components contained in the adhesive composition for surface protection sheets> By mixing polyurethane (A), multifunctional monomer (B), other monomers (C), photopolymerization initiator (D), fatty acid esters added if necessary, and other additives , And organic solvents to make adhesive compositions. The mixing method is not particularly limited. For example, it can be performed using a homogenizer or a stirring device equipped with a stirring blade such as a paddle and a blade.
又,可一次添加全部的成分進行混合,也可對每成分分成複數次重複添加及混合。又,常溫下,有固體的成分時,以溶解於溶劑者或分散於分散媒中者來添加或、以使加熱熔融者來添加等,此成分在黏著劑組成物中,容易以高的均勻性被混合。In addition, all the components may be added and mixed at once, or the addition and mixing may be repeated multiple times for each component. In addition, when there is a solid component at room temperature, it can be added with a solvent or dispersed in a dispersion medium or by heating and melting. This component is easy to be highly uniform in the adhesive composition. Sex is mixed.
<3.表面保護薄片> <3-1.表面保護薄片之構成> 本實施形態的表面保護薄片係在基材的單面上,形成包含上述黏著劑組成物之硬化物的黏著劑層。黏著劑層之厚度,較佳為3~150μm,更佳為5~130μm,又更佳為10~ 100μm。黏著劑層之膜厚為3μm以上時,黏著劑層之強度足夠,膜厚為150μm以下時,黏著劑層之膜厚之控制容易。 此外,欲將保護被黏物受衝撃的機能(耐衝撃性)賦予表面保護薄片時,黏著劑層之膜厚較佳為50μm以上。<3. Surface protection sheet> <3-1. Composition of surface protection sheet> The surface protection sheet of this embodiment is formed on one side of the base material to form an adhesive layer containing a cured product of the adhesive composition. The thickness of the adhesive layer is preferably 3 to 150 μm, more preferably 5 to 130 μm, and still more preferably 10 to 100 μm. When the film thickness of the adhesive layer is 3 μm or more, the strength of the adhesive layer is sufficient, and when the film thickness is 150 μm or less, the control of the film thickness of the adhesive layer is easy. In addition, when the function of protecting the adherend from impact (shock resistance) is to be imparted to the surface protection sheet, the film thickness of the adhesive layer is preferably 50 μm or more.
黏著劑層所含有之黏著劑組成物之硬化物的凝膠分率,較佳為85~100質量%,更佳為90~100質量%,又更佳為95~100質量%。在此,凝膠分率係指對溶劑之萃取不溶分的質量分率,在此,溶劑係選擇可溶解在黏著劑組成物之硬化物之中,未交聯的成分者。又,凝膠分率之具體的測量方法之例子係在實施例後述者。黏著劑組成物之硬化物之凝膠分率,只要是85~100質量%時,剝離表面保護薄片時,黏著劑層之一部分等殘留於被黏物,所謂的可抑制黏著劑殘留。The gel fraction of the cured product of the adhesive composition contained in the adhesive layer is preferably 85-100% by mass, more preferably 90-100% by mass, and still more preferably 95-100% by mass. Here, the gel fraction refers to the mass fraction of the solvent-extracted insoluble fraction. Here, the solvent is selected to be a non-crosslinked component that can be dissolved in the hardened substance of the adhesive composition. In addition, an example of a specific method for measuring the gel fraction is described later in the examples. When the gel fraction of the hardened substance of the adhesive composition is 85-100% by mass, when the surface protection sheet is peeled off, a part of the adhesive layer remains on the adherend, so-called adhesive residue can be suppressed.
基材之材質係依據表面保護薄片之用途可適宜選擇,可列舉例如樹脂薄膜。表面保護薄片,例如作為製造步驟中之保護薄片使用,檢查被黏物,亦即製品有時受傷或異物時,在保護薄片被積層的狀態進行時,基材為透明較佳。透明的基材,可列舉例如聚對苯二甲酸乙二酯、聚乙烯、聚丙烯、聚苯乙烯、聚醯亞胺、聚乙烯醇、聚氯乙烯、纖維素等。The material of the substrate can be appropriately selected according to the purpose of the surface protection sheet, and for example, a resin film can be mentioned. The surface protection sheet is used, for example, as a protection sheet in the manufacturing process. When inspecting adherends, that is, when the product is sometimes injured or foreign, when the protection sheet is laminated, the base material is preferably transparent. Examples of transparent substrates include polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and cellulose.
基材之厚度係依據表面保護薄片之用途可適宜選擇,無特別限定,樹脂薄膜時,基材之厚度,就操作性及強度的觀點,較佳為5μm以上,更佳為10μm以上,又更佳為20μm以上。又,考慮樹脂薄膜之可撓性時,基材的厚度,較佳為200μm以下,更佳為150μm以下,又更佳為100μm以下。The thickness of the substrate can be appropriately selected according to the application of the surface protection sheet, and is not particularly limited. In the case of a resin film, the thickness of the substrate is preferably 5 μm or more, more preferably 10 μm or more, and more from the viewpoint of handleability and strength. It is preferably 20 μm or more. Furthermore, when considering the flexibility of the resin film, the thickness of the substrate is preferably 200 μm or less, more preferably 150 μm or less, and still more preferably 100 μm or less.
又,作為基材,較佳為使用經抗靜電處理者。對基材施予的抗靜電處理,無特別限定,可使用在基材之至少單面設置抗靜電層的方法、對基材混入抗靜電劑的方法等。此外,在形成黏著劑層之基材面,必要時可實施酸處理、鹼處理、底塗處理、電暈處理、電漿處理、紫外線處理、臭氧處理等的易接著處理。Furthermore, as the substrate, it is preferable to use an antistatic treatment. The antistatic treatment applied to the substrate is not particularly limited, and a method of providing an antistatic layer on at least one side of the substrate, a method of mixing an antistatic agent on the substrate, and the like can be used. In addition, on the substrate surface where the adhesive layer is formed, easy bonding treatments such as acid treatment, alkali treatment, primer treatment, corona treatment, plasma treatment, ultraviolet treatment, ozone treatment, etc. can be carried out if necessary.
對於表面保護薄片,為了保護黏著劑層之目的,可在黏著劑層之表面積層分隔件。分隔件之材料,可使用例如紙、塑膠薄膜等,就表面平滑性優異的觀點,較佳為塑膠薄膜。作為分隔件使用之塑膠薄膜,只要是可保護上述黏著劑層者時,無特別限定,可列舉例如聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、聚丁烯等。For the surface protection sheet, for the purpose of protecting the adhesive layer, a separator can be layered on the surface area of the adhesive layer. For the material of the separator, for example, paper, plastic film, etc. can be used. In view of excellent surface smoothness, plastic film is preferred. The plastic film used as the separator is not particularly limited as long as it can protect the above-mentioned adhesive layer, and examples thereof include polyethylene, polypropylene, polyethylene terephthalate, and polybutylene.
<3-2.表面保護薄片之製造方法> 本實施形態之表面保護薄片之製造方法,例如在基材薄片上塗佈黏著劑組成物,積層分隔件後,對塗佈後之黏著劑組成物照射紫外線,藉由光硬化可得。<3-2. Manufacturing method of surface protection sheet> The manufacturing method of the surface protection sheet of this embodiment can be obtained by coating an adhesive composition on a substrate sheet, laminating a separator, and irradiating the coated adhesive composition with ultraviolet rays and curing by light.
在基材上塗佈黏著劑組成物的方法,無特別限定,可適宜選擇。例如,在基材上塗佈黏著劑組成物的方法,可列舉使用凹版輥塗佈機、逆輥塗佈機、輥吻式塗佈機、浸漬輥塗佈機、塗佈棒、刮刀塗佈機、噴霧塗佈機、缺角輪塗佈機、直接塗佈機等之各種塗佈機的方法、網版印刷法等。The method of coating the adhesive composition on the substrate is not particularly limited and can be appropriately selected. For example, the method of coating the adhesive composition on the substrate includes the use of a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a coating bar, and a knife coating. Various coating machine methods such as spray coating machine, cut-off wheel coating machine, direct coating machine, screen printing method, etc.
又,使黏著劑組成物光硬化時之光源,可列舉黑光(black light)、低壓水銀燈、高壓水銀燈、超高壓水銀燈、金屬鹵素燈、氙燈等。光之照射強度,只要是可使黏著劑組成物充分硬化即可,例如50~3000mW/cm2 為佳。又,光之照射強度較弱時,硬化需花費時間,故生產性降低。光照射為透明時,可由分隔件側、基材側之任一。In addition, the light source when the adhesive composition is cured by light includes black light, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, xenon lamp, and the like. The intensity of light irradiation is sufficient as long as the adhesive composition can be sufficiently hardened, for example, 50 to 3000 mW/cm 2 is preferred. In addition, when the intensity of light irradiation is weak, hardening takes time, so productivity is reduced. When the light irradiation is transparent, it can be either on the side of the separator or the side of the substrate.
<3-3.表面保護薄片之用途及所要求的性能> 檢查步驟中,製品或零件上被積層保護薄片的狀態下,要求可充分地發現或檢測製品或零件之微細的異物或受傷。又,保護薄片也適合使用為了保護作為智慧型手機、個人電腦、電視等之液晶顯示器等所使用的偏光板、波長板、相位差板、光學補償薄膜、反射薄片、亮度提昇薄膜等之光學元件使用之塑膠薄膜的表面。<3-3. Use of surface protection sheet and required performance> In the inspection step, it is required to fully detect or detect fine foreign objects or injuries of the product or part in the state where the protective sheet is laminated on the product or part. In addition, the protective sheet is also suitable for protecting optical elements such as polarizing plates, wave plates, retardation plates, optical compensation films, reflective sheets, brightness enhancement films, etc. used in liquid crystal displays of smart phones, personal computers, televisions, etc. The surface of the plastic film used.
本實施形態之表面保護薄片,作為此等的保護薄片使用時,被要求表面保護薄片為濁度少,亦即,霧度低。此時,表面保護薄片之霧度值,較佳為2.0%以下,更佳為1.5%以下,又更佳為1.0%以下。表面保護薄片之霧度值之具體的測量方法係在實施例中後述。When the surface protection sheet of this embodiment is used as such a protection sheet, it is required that the surface protection sheet has a low haze, that is, a low haze. At this time, the haze value of the surface protection sheet is preferably 2.0% or less, more preferably 1.5% or less, and still more preferably 1.0% or less. The specific measurement method of the haze value of the surface protection sheet is described later in the examples.
又,本實施形態之表面保護薄片,作為如上述之保護薄片使用時,表面保護薄片為了在輸送等之處理中,避免自製品或零件剝離,而需要最低限的剝離強度。而將表面保護薄片自製品或零件剝離時,為了使剝離的作業容易,或避免剝離中,使製品或零件變形或破損時,需要降低剝離強度。由此等觀點,表面保護薄片之剝離強度,當剝離速度為3.0m/分鐘時,雖因基材與黏著劑層之厚度而異,黏著劑層為50~100μm時,較佳為1~50gf/25mm,更佳為2~45gf/25mm,又更佳為3~40gf/25mm。表面保護薄片之剝離強度之具體的測量方法係如實施例所述。 [實施例]In addition, when the surface protection sheet of this embodiment is used as the above-mentioned protection sheet, the surface protection sheet needs the minimum peel strength in order to prevent the product or parts from peeling during processing such as transportation. When peeling the surface protection sheet from a product or part, it is necessary to reduce the peel strength in order to facilitate the peeling operation, or to avoid deformation or damage of the product or part during peeling. From this point of view, the peel strength of the surface protection sheet when the peel speed is 3.0m/min, although it varies with the thickness of the substrate and the adhesive layer, when the adhesive layer is 50-100μm, preferably 1-50gf /25mm, more preferably 2~45gf/25mm, still more preferably 3~40gf/25mm. The specific measurement method of the peel strength of the surface protection sheet is as described in the examples. [Example]
以下藉由實施例,詳細地說明本發明。本發明不受以下所示之實施例限定者。又,以下的實施例中,所得之聚胺基甲酸酯(A)之重量平均分子量係藉由膠體滲透層析儀(昭和電工股份公司製Shodex(註冊商標)GPC-101、以下作為GPC)所測量之聚苯乙烯換算之值。GPC之測量條件如下述。 管柱:昭和電工股份公司製LF-804 管柱溫度:40℃ 試料:聚胺基甲酸酯(A)之0.2質量%四氫呋喃溶液流量:1ml/分鐘 溶離液:四氫呋喃 檢測器:RI檢測器(示差折射率檢測器)The following examples illustrate the present invention in detail. The present invention is not limited by the examples shown below. In addition, in the following examples, the weight average molecular weight of the polyurethane (A) obtained is measured by a colloidal permeation chromatography (Shodex (registered trademark) GPC-101 manufactured by Showa Denko Co., Ltd., hereinafter referred to as GPC) The measured polystyrene conversion value. The measurement conditions of GPC are as follows. Column: Showa Denko Corporation LF-804 Column temperature: 40℃ Sample: 0.2% by mass tetrahydrofuran solution of polyurethane (A) Flow rate: 1ml/min Eluent: Tetrahydrofuran Detector: RI detector (differential refractive index detector)
<聚胺基甲酸酯(A)之合成> (A-1) 在具備有溫度計、攪拌器、滴下漏斗、附乾燥管之冷凝管的反應器中,投入二苯基甲烷二異氰酸酯之氫化物(Desmodur W、Sumika Covestro Urethane製)5.5kg(21mol)、及羥基價為56mgKOH/g,在末端具有羥基的聚丙二醇 ACTCOL D-2000(三井化學製、數平均分子量2000)40.1kg(20mol)。然後,反應器昇溫至60℃,使反應4小時,得到兩末端具有異氰酸酯基的聚胺基甲酸酯。<Synthesis of Polyurethane (A)> (A-1) In a reactor equipped with a thermometer, a stirrer, a dropping funnel, and a condenser tube with a drying tube, put in the hydride of diphenylmethane diisocyanate (manufactured by Desmodur W, Sumika Covestro Urethane) 5.5 kg (21 mol), and hydroxyl value It is 56 mgKOH/g and 40.1 kg (20 mol) of polypropylene glycol ACTCOL D-2000 (manufactured by Mitsui Chemicals, number average molecular weight 2000) having a hydroxyl group at the terminal. Then, the reactor was heated to 60° C. and reacted for 4 hours to obtain a polyurethane having isocyanate groups at both ends.
接著,反應器中加入2-羥基乙基丙烯酸酯232.2g(2mol),昇溫至70℃,使反應2小時,得到末端具有丙烯醯基的聚胺基甲酸酯(A-1)45.8kg。此聚胺基甲酸酯(A-1)藉由IR分析,確認來自異氰酸酯基之波峰消失。所得之聚胺基甲酸酯(A-1)的重量平均分子量為70,000。 因以IR確認來自異氰酸酯基之波峰消失,故在兩末端具有異氰酸酯基之聚胺基甲酸酯之全部末端加成有2-羥基乙基丙烯酸酯。亦即,以數基準,在聚胺基甲酸酯(A-1)所含有之聚胺基甲酸酯分子之末端之100%被導入丙烯醯基。Next, 232.2 g (2 mol) of 2-hydroxyethyl acrylate was added to the reactor, the temperature was raised to 70°C, and the reaction was performed for 2 hours to obtain 45.8 kg of polyurethane (A-1) having an acryl group at the terminal. The IR analysis of this polyurethane (A-1) confirmed that the peak derived from the isocyanate group disappeared. The weight average molecular weight of the obtained polyurethane (A-1) was 70,000. Since it was confirmed by IR that the peaks derived from the isocyanate group disappeared, 2-hydroxyethyl acrylate was added to all the ends of the polyurethane having isocyanate groups at both ends. That is, on a numerical basis, 100% of the ends of the polyurethane molecules contained in the polyurethane (A-1) are introduced with acryl groups.
(A-2) 除了使用異佛爾酮二異氰酸酯(DesmodurI、Sumika Covestro Urethane製)取代二苯基甲烷二異氰酸酯之氫化物外,與聚胺基甲酸酯(A-1)之合成法同樣得到在兩末端具有丙烯醯基的聚胺基甲酸酯(A-2)。所得之聚胺基甲酸酯(A-2)之重量平均分子量為67,000。(A-2) Except for the use of isophorone diisocyanate (Desmodur I, Sumika Covestro Urethane) to replace the hydrogenated diphenylmethane diisocyanate, the same method as the synthesis of polyurethane (A-1) is obtained with propylene at both ends Polyurethane of acyl group (A-2). The weight average molecular weight of the obtained polyurethane (A-2) was 67,000.
(A-3) 除了將二苯基甲烷二異氰酸酯之氫化物改變成8mol,及羥基價為56mgKOH/g之末端具有羥基之聚丙二醇 ACTCOL D-2000(三井化學製、數平均分子量2000)改變成7mol外,與聚胺基甲酸酯(A-1)之合成法同樣得到在兩末端具有丙烯醯基的聚胺基甲酸酯(A-3)。所得之聚胺基甲酸酯(A-3)之重量平均分子量為35,000。(A-3) In addition to changing the hydride of diphenylmethane diisocyanate to 8mol, and the polypropylene glycol ACTCOL D-2000 (manufactured by Mitsui Chemicals, number average molecular weight 2000) with a hydroxyl value of 56mgKOH/g and a hydroxyl value of 56mgKOH/g to 7mol, The method of synthesizing the urethane (A-1) similarly obtains the polyurethane (A-3) having acryl groups at both ends. The weight average molecular weight of the obtained polyurethane (A-3) was 35,000.
(A-4) 除了將二苯基甲烷二異氰酸酯之氫化物改變成4mol,羥基價為56mgKOH/g之末端具有羥基之聚丙二醇ACTCOL D-2000(三井化學製)改變成3mol外,與聚胺基甲酸酯(A-1)之合成法同樣得到在末端具有丙烯醯基的聚胺基甲酸酯(A-4)。所得之聚胺基甲酸酯(A-4)之重量平均分子量為12,000。(A-4) In addition to changing the hydride of diphenylmethane diisocyanate to 4mol, the hydroxyl value of 56mgKOH/g of polypropylene glycol ACTCOL D-2000 (manufactured by Mitsui Chemicals) with a hydroxyl group at the end was changed to 3mol, and polyurethane ( The synthesis method of A-1) similarly obtained polyurethane (A-4) having an acryl group at the terminal. The weight average molecular weight of the obtained polyurethane (A-4) was 12,000.
(A-5) 除了使用2-羥基乙基丙烯酸酯1.8mol與1-辛醇0.2mol,取代2-羥基乙基丙烯酸酯2mol外,與聚胺基甲酸酯(A-1)之合成法同樣得到在兩末端或單末端具有丙烯醯基之聚胺基甲酸酯混合物的聚胺基甲酸酯(A-5)。所得之聚胺基甲酸酯(A-5)之重量平均分子量為69,000。 因以IR確認來自異氰酸酯基之波峰消失,故在兩末端具有異氰酸酯基之聚胺基甲酸酯之全部末端加成有2-羥基乙基丙烯酸酯或1-辛醇。亦即,以數基準,在聚胺基甲酸酯(A-5)所含有之聚胺基甲酸酯分子之末端之90%被導入丙烯醯基。 此時,聚胺基甲酸酯(A-5)所含有之聚胺基甲酸酯(a1)以數基準為聚胺基甲酸酯(A)之80%,聚胺基甲酸酯(a2)以數基準為聚胺基甲酸酯(A)之20%。(A-5) Except for using 1.8 mol of 2-hydroxyethyl acrylate and 0.2 mol of 1-octanol, and 2 mol of substituted 2-hydroxyethyl acrylate, the same method as the synthesis of polyurethane (A-1) is obtained at both ends Or a polyurethane (A-5) which is a mixture of polyurethanes with an acrylic group at one end. The weight average molecular weight of the obtained polyurethane (A-5) was 69,000. Since it was confirmed by IR that the peaks derived from the isocyanate group disappeared, 2-hydroxyethyl acrylate or 1-octanol was added to all the ends of the polyurethane having isocyanate groups at both ends. That is, on a numerical basis, 90% of the ends of the polyurethane molecules contained in the polyurethane (A-5) are introduced with acryl groups. At this time, the polyurethane (a1) contained in the polyurethane (A-5) is 80% of the polyurethane (A) on a numerical basis, and the polyurethane ( a2) 20% of polyurethane (A) on a numerical basis.
<表面保護薄片用黏著劑組成物之調製> 以表1所記載的組成調配聚胺基甲酸酯樹脂(A)、多官能單體(B)、其他的單體(C)、光聚合起始劑(D)及添加劑,在25℃下,使用分散機混合,調製實施例1~9、比較例1~4的黏著劑組成物。<Preparation of adhesive composition for surface protection sheet> Polyurethane resin (A), polyfunctional monomer (B), other monomers (C), photopolymerization initiator (D), and additives were prepared with the composition described in Table 1, at 25°C , Using a disperser to mix to prepare the adhesive compositions of Examples 1 to 9 and Comparative Examples 1 to 4.
<表面保護薄片之製作> 對於實施例1~9及比較例1~4,以相同的方法,製作在單面具有光學用PET薄膜之基材的表面保護薄片。首先,使用塗佈器將調製後之黏著劑組成物塗佈於作為分隔件之厚度75μm的光學用PET薄膜(東洋紡股份公司製A4300)上,由被塗佈之黏著劑組成物上覆蓋厚度75μm之剝離PET薄膜(東洋紡股份公司製E7006)。其次,使用紫外線照射裝置(EYE GRAPHICS股份公司製、UV照射裝置3kW、高壓水銀燈),將被剝離PET薄膜覆蓋的薄片由剝離PET薄膜側面照射紫外線,使黏著劑組成物進行光硬化。紫外線之照射距離為25cm,燈移動速度為1.0m/分鐘,照射量為1000mJ/cm2 。硬化後之黏著劑層的厚度係使用厚度規(Dial gauge),測量剝離分隔件後之表面保護薄片的厚度後,由此測量值減去基材厚度75μm計算得到。厚度規之測量面為直徑5mm之圓形平面,且測量力為0.8N。實施例1~9、比較例1~4均為75μm。<Production of surface protection sheet> In the same manner as in Examples 1 to 9 and Comparative Examples 1 to 4, a surface protection sheet having a substrate of a PET film for optics on one side was produced. First, use an applicator to apply the prepared adhesive composition on a 75μm-thick optical PET film (A4300 manufactured by Toyobo Co., Ltd.) as a separator, and cover the coated adhesive composition with a thickness of 75μm Peeling PET film (E7006 manufactured by Toyobo Co., Ltd.). Next, using an ultraviolet irradiation device (manufactured by EYE GRAPHICS Co., Ltd., UV irradiation device 3kW, high-pressure mercury lamp), the sheet covered with the peeled PET film was irradiated with ultraviolet rays from the side of the peeled PET film to light-cur the adhesive composition. The irradiation distance of ultraviolet rays is 25cm, the moving speed of the lamp is 1.0m/min, and the irradiation amount is 1000mJ/cm 2 . The thickness of the adhesive layer after curing is calculated by using a dial gauge to measure the thickness of the surface protection sheet after peeling off the separator, and subtracting the thickness of the base material from 75 μm from the measured value. The measuring surface of the thickness gauge is a circular plane with a diameter of 5mm, and the measuring force is 0.8N. Examples 1 to 9 and Comparative Examples 1 to 4 are all 75 μm.
<表面保護薄片用黏著劑組成物及表面保護薄片之評價> 關於實施例1~9及比較例1~4之黏著劑組成物及表面保護薄片,藉由以下所記載的方法評價凝膠分率、透明性(霧度值)、剝離強度、積層性(潤濕性)、對被黏物之黏著劑殘留、及切斷時之黏著劑層的龜裂。結果示於表1。<Evaluation of adhesive composition for surface protection sheet and surface protection sheet> Regarding the adhesive compositions and surface protection sheets of Examples 1 to 9 and Comparative Examples 1 to 4, the gel fraction, transparency (haze value), peel strength, and layering properties (moisturizing) were evaluated by the methods described below. Wetness), the adhesive residue on the adherend, and the cracking of the adhesive layer during cutting. The results are shown in Table 1.
(凝膠分率) 首先,使用塗佈器,將實施例1~9及比較例1~4之各自的黏著劑組成物塗佈於50μm厚之剝離PET薄膜(東山薄膜股份公司製HY-S10),使硬化後之黏著劑層的厚度成為75μm。又,黏著劑層之厚度之確認方法係與表面保護薄片之製作項的上述測量方法同樣。(Gel fraction) First, using an applicator, the adhesive composition of each of Examples 1 to 9 and Comparative Examples 1 to 4 was applied to a 50μm thick peeling PET film (HY-S10 manufactured by Higashiyama Film Co., Ltd.), and cured. The thickness of the adhesive layer was 75 μm. In addition, the method of confirming the thickness of the adhesive layer is the same as the above-mentioned measuring method in the production of the surface protection sheet.
其次,自上述剝離PET薄膜上之黏著劑組成物上,以75μm厚的剝離PET薄膜(東洋紡股份公司製E7006)覆蓋。接著,使用紫外線照射裝置(EYE GRAPHICS股份公司製、UV照射裝置3kW、高壓水銀燈),將兩面以剝離PET薄膜覆蓋的黏著劑組成物由75μm厚之剝離PET薄膜側的面照射紫外線,使黏著劑組成物進行光硬化。紫外線之照射距離為25cm,燈移動速度為1.0m/分鐘,照射量為1000mJ/cm2 。Next, the adhesive composition on the peelable PET film was covered with a 75 μm thick peelable PET film (E7006 manufactured by Toyobo Co., Ltd.). Next, using an ultraviolet irradiation device (manufactured by EYE GRAPHICS Co., Ltd., UV irradiation device 3kW, high-pressure mercury lamp), the adhesive composition covered with peeling PET film on both sides was irradiated with ultraviolet light from the surface of the peeling PET film with a thickness of 75 μm to make the adhesive The composition is photocured. The irradiation distance of ultraviolet rays is 25cm, the moving speed of the lamp is 1.0m/min, and the irradiation amount is 1000mJ/cm 2 .
將製作後的薄片裁切成100mm×100mm之大小,自黏著劑組成物之硬化物剝離兩面剝離PET薄膜,作為測量用樣品。將此測量用樣品於50ml之甲苯中,25℃下浸漬24小時後,以80℃乾燥5小時,由甲苯浸漬前後之測量用樣品的質量,藉由下述式(1)算出凝膠分率。結果示於表1。 凝膠分率(質量%)=[A/B]×100 (1) A:測量用樣品之甲苯浸漬後中之乾燥質量(不含甲苯的質量)B:測量用樣品之甲苯浸漬前的質量The produced sheet was cut into a size of 100mm×100mm, and the PET film was peeled off from both sides of the hardened product of the adhesive composition, as a sample for measurement. The sample for measurement was immersed in 50 ml of toluene for 24 hours at 25°C, and then dried at 80°C for 5 hours. From the mass of the sample for measurement before and after the toluene immersion, the gel fraction was calculated by the following formula (1) . The results are shown in Table 1. Gel fraction (mass%)=[A/B]×100 (1) A: The dry mass of the measuring sample after immersion in toluene (the mass without toluene) B: The mass of the measuring sample before immersion in toluene
(霧度值) 將實施例1~9及比較例1~4各自製作之附分隔件的表面保護薄片裁切成50mm×50mm的大小,將剝離PET薄膜剝離。然後,將露出之黏著劑層的全面積層於玻璃板,使質量2kg(荷重19.6N)之橡膠滾輪(直徑:85mm、寬:50mm)1次往返,製作測量用樣品。關於此測量用樣品,使用霧度計(NM-150(股份公司村上色彩技術研究所製))測量霧度值。霧度值(%)係將擴散穿透率除以全光穿透率,乘上100計算得到。又,測量係對相同樣品測量3處,彼等的平均值作為霧度值。(Haze value) The surface protection sheets with separators produced in Examples 1 to 9 and Comparative Examples 1 to 4 were cut into a size of 50 mm×50 mm, and the peeling PET film was peeled off. Then, the entire area of the exposed adhesive layer was layered on the glass plate, and a rubber roller (diameter: 85 mm, width: 50 mm) with a mass of 2 kg (load 19.6 N) was reciprocated once to prepare a sample for measurement. Regarding this measurement sample, the haze value was measured using a haze meter (NM-150 (manufactured by Murakami Color Technology Research Co., Ltd.)). The haze value (%) is calculated by dividing the diffuse transmittance by the total light transmittance and multiplying by 100. In addition, the measurement system measures 3 places on the same sample, and their average value is used as the haze value.
(剝離強度) 將實施例1~9及比較例1~4各自製作之附分隔件的表面保護薄片裁切成25mm×150mm的大小,將剝離PET薄膜剝離。然後,將露出之黏著劑層的全面積層於玻璃板,使質量2kg(荷重19.6N)之橡膠滾輪(直徑:85mm、寬:50mm)1次往返,製作測量用樣品。 將所得之測量用樣品在溫度23℃及相對濕度50%之環境下放置1小時。然後,依據JIS K 6854-2,以剝離速度0.3m/分鐘、及3.0m/分鐘,進行180°方向之拉伸試驗,測量表面保護薄片對玻璃板的剝離強度(gf/25mm)。(Peel strength) The separator-attached surface protection sheets produced in each of Examples 1 to 9 and Comparative Examples 1 to 4 were cut into a size of 25 mm×150 mm, and the peeling PET film was peeled off. Then, the entire area of the exposed adhesive layer was layered on the glass plate, and a rubber roller (diameter: 85 mm, width: 50 mm) with a mass of 2 kg (load 19.6 N) was reciprocated once to prepare a sample for measurement. Place the resulting measurement sample in an environment with a temperature of 23°C and a relative humidity of 50% for 1 hour. Then, in accordance with JIS K 6854-2, a 180° direction tensile test was performed at a peeling speed of 0.3 m/min and 3.0 m/min, and the peel strength (gf/25mm) of the surface protection sheet to the glass plate was measured.
(積層性)
圖1為表示表面保護薄片10之積層性評價方法的平面圖,圖2為圖1中之A-A剖面圖。將附分隔件之表面保護薄片10裁切成20mm×100mm之大小,將剝離PET薄膜剝離。其次,在由表面保護薄片10之長度方向之一端至15mm為止的範圍,將黏著劑層12貼合於玻璃板30,黏著部分固定於玻璃板30,如圖2所示,提起表面保護薄片10之另一端。黏著部分的固定方法係如圖1所示,在由表面保護薄片10之上述一端至15mm為止的範圍,使表面保護薄片10之上面,且表面保護薄片之寬方向之兩外側,覆蓋玻璃板的方式黏貼玻璃紙膠帶20。(Layered)
Fig. 1 is a plan view showing a method of evaluating the layering of the
自此狀態放開表面保護薄片10之另一端,測量以表面保護薄片10之自身重量,使黏著劑層全體密著於玻璃板30為止的時間,使用下述基準評價實施例1~9及比較例1~4之表面保護薄片的積層性。
(積層性之評價基準)
◎:密著為止,未達5秒
○:密著為止,5秒以上、未達10秒
△:密著為止,10秒以上、未達15秒
×:密著為止,15秒以上、或未密著From this state, the other end of the
(黏著劑殘留) 將實施例1~9及比較例1~4各自製作之附分隔件的表面保護薄片裁切成50mm×50mm的大小,將剝離PET薄膜剝離。然後,將露出之黏著面積層於玻璃板,此作為樣品。此樣品在85℃、相對濕度85%下放置3日後,自玻璃板剝離表面保護薄片,以目視確認對玻璃板之表面的黏著劑殘留,使用下述基準評價。(Adhesive residue) The surface protection sheets with separators produced in Examples 1 to 9 and Comparative Examples 1 to 4 were cut into a size of 50 mm×50 mm, and the peeling PET film was peeled off. Then, the exposed adhesive area was layered on a glass plate, which was used as a sample. After this sample was left at 85°C and 85% relative humidity for 3 days, the surface protection sheet was peeled off from the glass plate, the adhesive residue on the surface of the glass plate was visually confirmed, and the following criteria were used for evaluation.
(黏著劑殘留之評價基準) ○:玻璃板之表面,與貼合前比較無變化。 △:玻璃板之表面,確認稍微有黏著劑殘留。 ×:玻璃板之表面,確認明顯有黏著劑殘留。(Evaluation criteria for adhesive residue) ○: The surface of the glass plate has no change compared with that before bonding. △: On the surface of the glass plate, a slight adhesive residue was confirmed. ×: On the surface of the glass plate, the adhesive residue was confirmed.
(切斷時之黏著劑層之龜裂) 將實施例1~9及比較例1~4各自製作之表面保護薄片使用鋸齒刀(刀高:0.80mm、刀角:50°(股份公司塚谷刀物製作所製))切斷,切斷後之黏著劑層的端面使用顯微鏡(倍率:800倍(股份公司hirox製 RH-2000)),使用下述基準評價。(Crack in the adhesive layer when cut) The surface protection sheets produced in each of Examples 1 to 9 and Comparative Examples 1 to 4 were cut with a serrated knife (knife height: 0.80 mm, knife angle: 50° (manufactured by Tsukadani Tomo Seisakusho Co., Ltd.)) and adhered after cutting The end surface of the agent layer was evaluated using a microscope (magnification: 800 times (RH-2000 manufactured by Hirox Co., Ltd.)), and the following criteria were used.
(龜裂之評價基準) ○:黏著劑層,確認龜裂。 ×:黏著劑層,未確認龜裂。(Crack evaluation criteria) ○: The adhesive layer was cracked. ×: The adhesive layer has no cracks.
<實施例及比較例之評價結果> 依據以上的實施例及比較例時,聚胺基甲酸酯(A)之含量為10質量%之比較例1的組成物看見黏著劑殘留。又,作為聚胺基甲酸酯(A),使用重量平均分子量為12000之聚胺基甲酸酯(A-4)之比較例2的組成物,其積層性不足,也看見黏著劑殘留。此外,不含多官能單體(B)之比較例3的組成物,剝離強度過高,積層性也不足。多官能單體(B)為15質量%之比較例4的組成物,黏著劑層硬,切斷時黏著劑層產生龜裂。<Evaluation results of Examples and Comparative Examples> According to the above Examples and Comparative Examples, the composition of Comparative Example 1 in which the content of the polyurethane (A) is 10% by mass, the adhesive remains. In addition, the composition of Comparative Example 2 in which a polyurethane (A-4) with a weight average molecular weight of 12,000 was used as the polyurethane (A) had insufficient layering properties, and adhesive residue was also seen. In addition, the composition of Comparative Example 3 that does not contain the polyfunctional monomer (B) had too high peel strength and insufficient layering properties. The polyfunctional monomer (B) was 15% by mass in the composition of Comparative Example 4, and the adhesive layer was hard, and cracks occurred in the adhesive layer during cutting.
10:表面保護薄片 12:黏著劑層 14:基材 20:玻璃紙膠帶 30:玻璃板10: Surface protection sheet 12: Adhesive layer 14: Substrate 20: Cellophane tape 30: glass plate
[圖1] 表示表面保護薄片之積層性評價方法的平面圖。 [圖2] 圖1中之A-A剖面圖。[Figure 1] A plan view showing a method for evaluating the layering properties of a surface protection sheet. [Figure 2] A-A section view in Figure 1.
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JP6251687B2 (en) * | 2012-12-19 | 2017-12-20 | 昭和電工株式会社 | Adhesive composition for optical film and surface protective film |
JP6097132B2 (en) * | 2013-04-22 | 2017-03-15 | 昭和電工株式会社 | Photocurable composition for transparent adhesive sheet, adhesive sheet using the same, and use thereof |
JP6249565B2 (en) * | 2014-05-02 | 2017-12-20 | 昭和電工株式会社 | Thermal insulating adhesive composition |
TWI601798B (en) | 2014-06-18 | 2017-10-11 | 昭和電工股份有限公司 | Photo-curable composition for a transparent adhesive sheet, transparent adhesive sheet |
KR20170023717A (en) * | 2015-08-24 | 2017-03-06 | 닛토덴코 가부시키가이샤 | Optical member with surface protection film |
JP2018053212A (en) * | 2016-09-30 | 2018-04-05 | 日立化成株式会社 | Adhesive film |
JP7012427B2 (en) * | 2016-12-15 | 2022-02-14 | 昭和電工株式会社 | Photocurable composition and adhesive sheet |
KR102253912B1 (en) * | 2017-10-05 | 2021-05-20 | 쇼와 덴코 가부시키가이샤 | Adhesive composition and adhesive sheet |
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- 2019-09-20 CN CN201980062650.XA patent/CN112752817A/en active Pending
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TWI824013B (en) | 2023-12-01 |
CN112752817A (en) | 2021-05-04 |
WO2020066866A1 (en) | 2020-04-02 |
JP7380577B2 (en) | 2023-11-15 |
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