TWI623560B - Novel polyester polyurethane polyol, two-liquid type laminating adhesive polyol, resin composition, curable resin composition, two-liquid type laminating adhesive, and solar cell back sheet - Google Patents
Novel polyester polyurethane polyol, two-liquid type laminating adhesive polyol, resin composition, curable resin composition, two-liquid type laminating adhesive, and solar cell back sheet Download PDFInfo
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Abstract
本發明提供濕熱條件下的基材接著性得到飛躍性改善、並且在長期使用時由紫外線造成的變色、基材接著性的劣化少的太陽能電池用背板接著劑。一種新穎聚酯聚胺酯多元醇，作為含有新穎聚酯聚胺酯多元醇的雙液型疊層接著劑的主劑使用，其特徵在於具有使：使支鏈亞烷基多元醇與脂肪族二羧酸或其烷基酯反應而得到的脂肪族聚酯多元醇(i)、脂肪族多官能異氰酸酯化合物(ii)和碳原子數2~13的脂肪族二醇(iii)反應而得到的樹脂結構。The present invention provides a solar cell backsheet adhesive agent that has dramatically improved substrate adhesion under moist heat conditions, and has discoloration caused by ultraviolet rays during long-term use and has little deterioration in substrate adhesion. A novel polyester polyurethane polyol is used as a main agent of a two-liquid type laminating adhesive containing the novel polyester polyurethane polyol, and is characterized in that: a branched alkylene polyol is mixed with an aliphatic dicarboxylic acid or A resin structure obtained by reacting an aliphatic polyester polyol (i), an aliphatic polyfunctional isocyanate compound (ii) obtained by reacting an alkyl ester thereof, and an aliphatic diol (iii) having 2 to 13 carbon atoms.
Description
本發明涉及濕熱條件下的基材接著性和耐紫外線性優異的太陽能電池用背板、作為該背板用接著劑有用的雙液型疊層用接著劑、構成該接著劑的硬化性樹脂組成物、構成其主劑的新穎聚酯聚胺酯多元醇和雙液型疊層接著劑用多元醇劑、以及樹脂組成物。The present invention relates to a back sheet for a solar cell having excellent substrate adhesion and ultraviolet resistance under moist heat conditions, a two-liquid type laminating adhesive useful as the back sheet adhesive, and a curable resin composition constituting the adhesive. Products, novel polyester polyurethane polyols and main components of the novel polyester polyols, two-component laminating adhesives, and resin compositions.
近年來，以石油、煤為代表的化石燃料的枯竭受到擔心，用於確保由這些化石燃料得到的替代能源的開發成為當務之急。該化石燃料替代能源中，能夠將太陽能直接轉換為電能的太陽能發電作為半永久且無公害的新穎能源已得到實用化，並且在實際利用方面的性價比的提高驚人，作為清潔的能源的期待非常高。In recent years, the depletion of fossil fuels typified by petroleum and coal has been feared, and the development of alternative energy sources obtained from these fossil fuels has become an urgent task. Among the fossil fuel alternative energy sources, solar power generation capable of directly converting solar energy into electrical energy has been put into practical use as a semi-permanent and pollution-free novel energy source, and the cost-effectiveness in practical utilization has been astonishingly increased, and expectations for clean energy sources are very high.
太陽能發電中使用的太陽能電池構成了將太陽光的能量直接轉換為電能的太陽能發電系統的心臟部，其由以矽等為代表的半導體構成，其結構中，將太陽能電池元件以串聯、並聯方式佈線，為了保護該元件而實施了各種封裝且被單元化。被組裝入這樣的封裝的單元被稱為太陽能電池模組，且通常成為下述構成：形成由玻璃覆蓋照射到太陽光的面，由包含熱塑性樹脂的填充材料填埋間隙，由密封片保護背面。作為包含熱塑性樹脂的填充材料，出於透明性高、耐濕性也優異的理由，多使用乙烯-乙酸乙烯酯共聚樹脂。另一方面，背面保護片(背板)要求機械強度、耐候性、耐熱性、耐濕熱性、耐光性等特性。這樣的太陽能電池模組通常要在室外使用長達30年左右的時間，因此構成背板的接著劑要求具有長期可靠性的接著強度，具體而言，要求對聚酯膜、聚氟代乙烯膜等具有不同特徵的各種膜的高接著性、用於在露天環境下也長期維持接著性的耐濕熱性高的水準。The solar cell used in solar power generation constitutes the heart of a solar power generation system that directly converts the energy of sunlight into electrical energy. It consists of a semiconductor such as silicon. In its structure, solar cell elements are connected in series and parallel. In order to protect this element, wiring is implemented in various packages and is unitized. A unit assembled into such a package is called a solar cell module, and generally has a structure in which a surface covered with glass is irradiated with sunlight, a gap is filled with a filler containing a thermoplastic resin, and a back surface is protected by a sealing sheet. . As a filler containing a thermoplastic resin, an ethylene-vinyl acetate copolymer resin is often used for reasons of high transparency and excellent moisture resistance. On the other hand, the back protective sheet (back sheet) requires properties such as mechanical strength, weather resistance, heat resistance, heat and humidity resistance, and light resistance. Such solar cell modules are generally used outdoors for about 30 years. Therefore, the adhesive constituting the back sheet requires long-term reliable bonding strength. Specifically, polyester films and polyvinyl fluoride films are required. It has high adhesiveness of various films with different characteristics, and a high level of humidity and heat resistance for long-term maintenance of adhesiveness even in an open-air environment.
已知如下的技術：作為這樣的背板用接著劑，例如將芳香族二元酸、C9以上的脂肪族羧酸和C5以上的脂肪族醇用作原料單體的高分子量聚酯多元醇、以及並用低分子量聚酯聚胺酯多元醇作為主劑，並且使用多異氰酸酯化合物作為硬化劑，由此使起因於芳香族二元酸的樹脂的凝聚力提高、並且藉由長鏈脂肪族醇使酯鍵間距伸長從而抑制水分浸入由此來改善耐濕熱性，同時藉由並用低分子量胺基甲酸酯來改善塗佈性、潤濕性(參照下述專利文獻1)。As such a backsheet adhesive, for example, a high molecular weight polyester polyol using an aromatic dibasic acid, an aliphatic carboxylic acid of C9 or higher, and an aliphatic alcohol of C5 or higher as a raw material monomer, By using a low molecular weight polyester polyurethane polyol as a main agent and a polyisocyanate compound as a hardener, the cohesion of a resin derived from an aromatic dibasic acid is improved, and the ester bond distance is increased by a long-chain aliphatic alcohol. The elongation suppresses the penetration of moisture to improve the heat and humidity resistance, and at the same time, the low-molecular-weight urethane is used to improve the coatability and wettability (see Patent Document 1 below).
但是，對於背板的外部裝飾用膜而言，近年來開發出了各種結構且提高了外觀設計性的太陽能電池，此時，接著劑層要求具有不引起由紫外線造成的劣化的功能，但是該專利文獻1記載的接著劑雖然對於背板自身的耐濕性、耐候性而言是良好的，但還沒有達到充分的水準，另外其無法避免在室外長期使用時由紫外線造成的變色、接著力的下降。 【先前技術文獻】 【專利文獻】However, with regard to films for exterior decoration of backsheets, various structures have been developed in recent years to improve the design of solar cells. At this time, the adhesive layer is required to have a function that does not cause deterioration due to ultraviolet rays. Although the adhesive described in Patent Document 1 is good for the moisture resistance and weather resistance of the back sheet itself, it has not yet reached a sufficient level, and it cannot avoid discoloration and adhesion caused by ultraviolet rays during long-term outdoor use. Decline. [Prior Art Literature] [Patent Literature]
【專利文獻1】：日本專利第4416047號公報[Patent Document 1]: Japanese Patent No. 4416047
【發明待解決的問題】[Invention to be solved]
因此，本發明要解決的課題在於提供濕熱條件下的基材接著性得到飛躍性改善、並且在長期使用時由紫外線造成的變色、基材接著性的劣化少的雙液型疊層用接著劑、構成該接著劑的硬化性樹脂組成物、該接著劑的主劑成分、構成該接著劑的主劑成分的新穎聚酯聚胺酯多元醇、以及表現出耐濕熱性和耐變色性優異的性能的太陽能電池用背板。 【解決問題的手段】Therefore, the problem to be solved by the present invention is to provide a two-liquid type laminating adhesive with greatly improved substrate adhesion under moist heat conditions, and discoloration caused by ultraviolet rays during long-term use, and less deterioration of substrate adhesion. , A curable resin composition constituting the adhesive, a main agent component of the adhesive, a novel polyester polyurethane polyol constituting the main agent component of the adhesive, and a performance exhibiting excellent heat and moisture resistance and discoloration resistance Back sheet for solar cells. [Means to solve the problem]
本發明人等為了解決上述課題而進行了廣泛深入的研究，結果發現，一種聚酯多元醇，其具有使：使支鏈亞烷基多元醇與脂肪族二羧酸成分反應而得到的脂肪族聚酯多元醇與脂肪族多元異氰酸酯和碳原子數2~13的脂肪族二醇反應而得到的樹脂結構，其耐濕性極其優異，在將其用於太陽能電池用背板的外部裝飾膜用接著劑的主劑時，濕熱條件下的基劑密合性顯著優異，並且在室外長期使用時，能夠有效地防止起因於紫外線的黃變、接著性劣化，從而完成了本發明。The present inventors have conducted extensive and intensive studies in order to solve the above problems, and as a result, have found that a polyester polyol having an aliphatic obtained by reacting a branched alkylene polyol with an aliphatic dicarboxylic acid component The polyester structure reacts with an aliphatic polyisocyanate and an aliphatic diol having 2 to 13 carbon atoms. The resin structure is extremely excellent in moisture resistance. It is used for exterior decorative films of backsheets for solar cells. In the case of the main agent of the adhesive agent, the adhesiveness of the base agent under moist heat conditions is remarkably excellent, and when it is used outdoors for a long period of time, it can effectively prevent yellowing and deterioration of adhesiveness due to ultraviolet rays, thereby completing the present invention.
即，本發明涉及一種新穎聚酯聚胺酯多元醇，其特徵在於，具有使支鏈亞烷基多元醇與脂肪族二羧酸或其烷基酯反應而得到的脂肪族聚酯多元醇(i)、脂肪族多官能異氰酸酯化合物(ii)和碳原子數2~13的脂肪族二醇(iii)反應而得到的樹脂結構。That is, the present invention relates to a novel polyester polyurethane polyol having an aliphatic polyester polyol (i) obtained by reacting a branched alkylene polyol with an aliphatic dicarboxylic acid or an alkyl ester thereof. , A resin structure obtained by reacting an aliphatic polyfunctional isocyanate compound (ii) with an aliphatic diol (iii) having 2 to 13 carbon atoms.
本發明還涉及包含該新穎聚酯聚胺酯多元醇的雙液型疊層接著劑用多元醇劑。The present invention also relates to a polyol agent for a two-liquid type laminated adhesive containing the novel polyester polyurethane polyol.
本發明還涉及以該新穎聚酯聚胺酯多元醇(A)和多官能環氧化合物(B)為必要成分的樹脂組成物。The present invention also relates to a resin composition comprising the novel polyester polyurethane polyol (A) and a polyfunctional epoxy compound (B) as essential components.
本發明還涉及使用新穎聚酯聚胺酯二醇、或該樹脂組成物作為主劑、並且配合了脂肪族多異氰酸酯(D)作為硬化劑而成的硬化性樹脂組成物。The present invention also relates to a curable resin composition using a novel polyester urethane diol or the resin composition as a main agent and blending an aliphatic polyisocyanate (D) as a curing agent.
本發明還涉及包含硬化性樹脂組成物的雙液型疊層用接著劑。The present invention also relates to a two-liquid type laminating adhesive containing a curable resin composition.
本發明還涉及一種太陽能電池用背板，其由選自聚酯膜、氟系樹脂膜、聚烯烴膜、金屬箔中的1種以上的膜、和用於將這些膜互相貼合的包含該雙液型疊層用接著劑的接著層成形而成。 【發明之效果】The present invention also relates to a back sheet for a solar cell, which comprises one or more films selected from the group consisting of a polyester film, a fluororesin film, a polyolefin film, and a metal foil, and includes a film for bonding these films to each other. A two-liquid type laminate is formed by forming an adhesive layer. [Effect of the invention]
根據本發明，提供濕熱條件下的基材接著性得到飛躍性改善、並且在長期使用時由紫外線造成的變色、基材接著性的劣化少的雙液型疊層用接著劑、構成該接著劑的硬化性樹脂組成物、該接著劑的主劑成分、構成該接著劑的主劑成分的新穎聚酯聚胺酯多元醇、和表現出耐濕熱性、耐變色性優異的性能的太陽能電池用背板。According to the present invention, there is provided a two-liquid type laminating adhesive for laminating substrates with drastically improved adhesion under moist heat conditions, and discoloration due to ultraviolet rays during long-term use, and less deterioration in substrate adhesion, and the composition Curable resin composition, the main component of the adhesive, the novel polyester polyurethane polyol constituting the main component of the adhesive, and a back sheet for a solar cell that exhibits excellent performance in moisture and heat resistance and discoloration resistance .
本發明的新穎聚酯聚胺酯多元醇作為太陽能電池用背板接著劑的主劑即雙液型疊層接著劑用多元醇劑而有用，其使用支鏈亞烷基多元醇作為構成聚酯結構部位的原料二醇成分，因此該聚酯結構部位的耐水解性飛躍性地提高。另外，由於脂肪族性高，因此不易產生起因於紫外線的變色、接著劣化，並且接著力由於胺基甲酸酯鍵的凝聚力而提高。The novel polyester polyurethane polyol of the present invention is useful as a polyol agent for a two-liquid laminated adhesive, which is a main agent of a back sheet adhesive for solar cells. It uses a branched alkylene polyol as a polyester structure site. As a raw material diol component, the hydrolysis resistance of the polyester structural site is dramatically improved. In addition, since it is highly aliphatic, discoloration and subsequent deterioration due to ultraviolet rays are less likely to occur, and the adhesion force is improved by the cohesive force of the urethane bond.
在此，作為該新穎聚酯聚胺酯多元醇的主要原料成分的該脂肪族聚酯多元醇(i)，如上所述，具有使支鏈亞烷基多元醇與脂肪族二羧酸或其烷基酯反應而得到的結構。該支鏈亞烷基多元醇具體而言為分子結構中具有存在3級碳原子或4級碳原子的亞烷基結構的多元醇，例如可舉出：1,2-丙二醇、1,3-丁二醇、2-甲基-1,3-丙二醇、新戊二醇、3-甲基-1,5-戊二醇、2-正丁基-2-乙基-1,3-丙二醇、2,2-二甲基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、1,2-己二醇、1,2-辛二醇等支鏈烷烴二醇；三羥甲基丙烷、季戊四醇等3官能以上的含有支鏈烷烴結構的多官能醇。其中，從可得到與基材的塗佈性優異、並且耐濕熱性良好的接著劑的觀點出發，宜為碳原子數4~13的支鏈亞烷基二醇、特別宜為新戊二醇。另外，本發明中，藉由並用該支鏈烷烴二醇、和一部分3官能以上的含有支鏈烷烴結構的多官能醇，由此這些支鏈亞烷基多元醇能夠提高與基材的接著力、並且能夠控制該新穎聚酯聚胺酯多元醇的分子量分佈。此時，支鏈烷烴二醇、與該3官能以上的含有支鏈烷烴結構的多官能醇的使用比例，宜為質量比[支鏈烷烴二醇/3官能以上的含有支鏈烷烴結構的多官能醇]為99.5/0.5~95/5的比例。Here, as described above, the aliphatic polyester polyol (i), which is a main raw material component of the novel polyester polyurethane polyol, has a branched alkylene polyol and an aliphatic dicarboxylic acid or an alkyl group thereof, as described above. Structure obtained by ester reaction. The branched chain alkylene polyol is specifically a polyol having an alkylene structure having a third carbon atom or a fourth carbon atom in the molecular structure, and examples thereof include 1,2-propanediol, 1,3- Butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanedione Alcohols, branched-chain alkanediols such as 1,2-octanediol; trifunctional or higher-functional branched alkane-containing polyfunctional alcohols such as trimethylolpropane and pentaerythritol. Among them, branched alkylene glycols having 4 to 13 carbon atoms are preferred, and neopentyl glycol is particularly preferred from the viewpoint of obtaining an adhesive having excellent coatability with a substrate and good moisture and heat resistance. . In addition, in the present invention, by using the branched alkane diol and a part of a trifunctional or higher polyfunctional alcohol having a branched alkane structure in combination, these branched alkylene polyols can improve adhesion to a substrate. And can control the molecular weight distribution of the novel polyester polyurethane polyol. In this case, the ratio of the use of the branched alkane diol and the trifunctional or higher polyfunctional alcohol containing a branched alkane structure is preferably greater than the mass ratio of Functional alcohol] is a ratio of 99.5 / 0.5 to 95/5.
另一方面，就與其反應的脂肪族二羧酸或其烷基酯而言，作為直鏈狀脂肪族二羧酸，可舉出：丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十七烷二酸、十八烷二酸、十九烷二酸、二十烷二酸、或它們的碳原子數1~4的烷基酯等。On the other hand, as the aliphatic dicarboxylic acid or its alkyl ester which reacts with it, examples of the linear aliphatic dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanoic acid, hexadecanedioic acid Acids, heptadecanedioic acid, octadecenedioic acid, nonadecanedioic acid, eicosenedioic acid, or alkyl esters having 1 to 4 carbon atoms, and the like.
本發明中，它們中，從在作為接著劑使用時與基材的接著性和耐濕熱性良好的觀點出發，特別較佳為己二酸、壬二酸、癸二酸等碳原子數6~10的二羧酸。In the present invention, among them, from the viewpoint of good adhesion to the substrate and moist heat resistance when used as an adhesive, 6 to 6 carbon atoms such as adipic acid, azelaic acid, and sebacic acid are particularly preferred. 10 dicarboxylic acids.
另外，本發明中，出於使作為接著劑的柔軟性、潤濕性提高的目的，並且在不損害本發明的效果的範圍內，可以在上述各原料成分中進一步並用乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、1,8-壬二醇、二乙二醇等直鏈狀烷烴二醇。In addition, in the present invention, for the purpose of improving the flexibility and wettability as an adhesive, and within a range that does not impair the effects of the present invention, ethylene glycol, 1, and Linear alkanediols such as 3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-nonanediol, and diethylene glycol.
另外，出於調整該脂肪族聚酯多元醇(i)的分子量、黏度的目的，作為該聚酯聚胺酯多元醇(A)的原料，可以使用甲酸、乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十二烷酸、十四烷酸、十六烷酸、十七烷酸、十八烷酸等一元羧酸。In addition, for the purpose of adjusting the molecular weight and viscosity of the aliphatic polyester polyol (i), as the raw material of the polyester polyurethane polyol (A), formic acid, acetic acid, propionic acid, butyric acid, valeric acid, Monocarboxylic acids such as hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid.
接著，就使上述的支鏈亞烷基多元醇與脂肪族二羧酸或其烷基酯反應的條件而言，例如可舉出使支鏈亞烷基多元醇與脂肪族二羧酸或其烷基酯在酯化催化劑的存在下在160~270℃的溫度範圍內進行反應的方法。Next, the conditions for reacting the branched alkylene polyol described above with an aliphatic dicarboxylic acid or an alkyl ester thereof include, for example, the reaction of a branched alkylene polyol with an aliphatic dicarboxylic acid or an alkyl dicarboxylic acid. A method in which an alkyl ester is reacted in the temperature range of 160 to 270 ° C in the presence of an esterification catalyst.
從能夠使最終得到的新穎聚酯聚胺酯多元醇中羰氧基的量減少從而耐濕性提高、並且在使用最終得到的聚酯聚胺酯多元醇(A)作為接著劑用的主劑時可防止水浸入接著層且改善耐濕熱性的觀點出發，宜為上述得到的該脂肪族聚酯多元醇(i)的羥值處於100~130mg KOH/g的範圍。The moisture resistance can be improved by reducing the amount of carbonyloxy groups in the novel polyester polyurethane polyol finally obtained, and preventing water when using the finally obtained polyester polyurethane polyol (A) as a main agent for an adhesive. From the viewpoint of impregnating the adhesive layer and improving the heat and humidity resistance, the aliphatic polyester polyol (i) obtained as described above preferably has a hydroxyl value in the range of 100 to 130 mg KOH / g.
該新穎聚酯聚胺酯多元醇可藉由使這樣得到的脂肪族聚酯多元醇(i)與脂肪族多官能異氰酸酯化合物(ii)、和碳原子數2~13的脂肪族二醇(iii)反應來製造。The novel polyester polyurethane polyol can be obtained by reacting the aliphatic polyester polyol (i) thus obtained with an aliphatic polyfunctional isocyanate compound (ii) and an aliphatic diol (iii) having 2 to 13 carbon atoms. To make.
在此，就該脂肪族多官能異氰酸酯化合物(ii)而言，可舉出：脂肪族二異氰酸酯化合物(ii-1)、和3官能以上的脂肪族多異氰酸酯化合物(ii-2)。Here, the aliphatic polyfunctional isocyanate compound (ii) includes an aliphatic diisocyanate compound (ii-1) and a trifunctional or more functional aliphatic polyisocyanate compound (ii-2).
就該脂肪族二異氰酸酯化合物(ii-1)而言，例如可舉出：丁烷-1,4-二異氰酸酯、六亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、苯二亞甲基二異氰酸酯、間四甲基苯二亞甲基二異氰酸酯等脂肪族二異氰酸酯；Examples of the aliphatic diisocyanate compound (ii-1) include butane-1,4-diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene. Aliphatic diisocyanates such as diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate;
環己烷-1,4-二異氰酸酯、異佛爾酮二異氰酸酯、離氨酸二異氰酸酯、二環己基甲烷-4,4’-二異氰酸酯、1,3-二(異氰酸酯甲基)環己烷、甲基環己烷二異氰酸酯、異丙叉二環己基-4,4’-二異氰酸酯、降冰片烷二異氰酸酯等脂環族二異氰酸酯。Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane Alicyclic diisocyanates such as methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, norbornane diisocyanate.
另一方面，就該3官能以上的多異氰酸酯化合物(ii-2)而言，例如可舉出：分子內具有胺基甲酸酯鍵部位的加合型多異氰酸酯化合物、分子內具有異氰尿素酸酯環結構的氰尿素酸酯型多異氰酸酯化合物。On the other hand, examples of the tri- or more functional polyisocyanate compound (ii-2) include an addition type polyisocyanate compound having a urethane bond site in the molecule, and isocyanurate in the molecule. A cyanurate type polyisocyanate compound having an ester ring structure.
該分子內具有胺基甲酸酯鍵部位的加合型多異氰酸酯化合物例如可以藉由使該二異氰酸酯化合物(ii-1)與該脂肪族聚酯多元醇(i)反應來得到。The addition type polyisocyanate compound having a urethane bond site in the molecule can be obtained, for example, by reacting the diisocyanate compound (ii-1) with the aliphatic polyester polyol (i).
另外，該分子內具有異氰尿素酸酯環結構的氰尿素酸酯型多異氰酸酯化合物例如可以藉由使該脂肪族二異氰酸酯化合物(ii-1)在異氰脲酸酯化催化劑的存在下在40~100℃的溫度範圍進行反應來得到。The cyanurate-type polyisocyanate compound having an isocyanurate ring structure in the molecule can be obtained by, for example, allowing the aliphatic diisocyanate compound (ii-1) to be present in the presence of an isocyanuration catalyst. It is obtained by performing a reaction in a temperature range of 40 to 100 ° C.
在此，在使用該3官能以上的多異氰酸酯化合物(ii-2)時，該聚酯聚胺酯多元醇(A)的支鏈度提高，能夠使作為該太陽能電池背板用接著劑使用時的耐濕熱性進一步提高。Here, when the tri- or more functional polyisocyanate compound (ii-2) is used, the degree of branching of the polyester polyurethane polyol (A) is improved, and the resistance when used as an adhesive for a solar cell back sheet can be improved. Damp heat property is further improved.
以上詳述的該脂肪族多官能異氰酸酯化合物(ii)中，特別是從得到對基材的塗佈性、耐濕熱性優異、並且防止對紫外線的接著劣化的效果優異的接著劑的觀點出發，宜為異佛爾酮二異氰酸酯。In the aliphatic polyfunctional isocyanate compound (ii) detailed above, in particular, from the viewpoint of obtaining an adhesive that is excellent in coatability to a substrate, has excellent heat and humidity resistance, and has an excellent effect of preventing deterioration of ultraviolet rays, Should be isophorone diisocyanate.
另一方面，關於碳原子數2~13的脂肪族二醇(iii)，具體而言可舉出：乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、1,8-壬二醇、二乙二醇等直鏈狀烷烴二醇，或者該支鏈烷烴多元醇(i-1)。它們中，特別是從在作為接著劑使用時可得到與基材的接著性優異的接著劑的觀點出發，宜為碳原子數4~9的直鏈狀烷烴二醇，特別宜為1,6-己二醇。On the other hand, specific examples of the aliphatic diol (iii) having 2 to 13 carbon atoms include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexane. A linear alkane diol such as a diol, 1,8-nonanediol, and diethylene glycol, or the branched alkane polyol (i-1). Among them, a straight-chain alkanediol having 4 to 9 carbon atoms is preferred from the viewpoint that an adhesive having excellent adhesion to a substrate can be obtained when used as an adhesive, and particularly preferably 1,6 -Hexanediol.
就該脂肪族聚酯多元醇(i)、脂肪族多官能異氰酸酯化合物(ii)、和碳原子數2~13的脂肪族二醇(iii)的反應而言，例如可舉出：在使脂肪族聚酯多元醇(i)與脂肪族多官能異氰酸酯化合物(ii)反應後，接著使碳原子數2~13的脂肪族二醇(iii)進行反應的方法(方法1)，以及使脂肪族聚酯多元醇(i)、脂肪族多官能異氰酸酯化合物(ii)、和碳原子數2~13的脂肪族二醇(iii)同時進行反應的方法(方法2)。Examples of the reaction between the aliphatic polyester polyol (i), the aliphatic polyfunctional isocyanate compound (ii), and the aliphatic diol (iii) having 2 to 13 carbon atoms include the following: A method (method 1) of reacting an aliphatic polyester polyol (i) with an aliphatic polyfunctional isocyanate compound (ii) and then reacting an aliphatic diol (iii) having 2 to 13 carbon atoms (method 1), and an aliphatic Method for simultaneously reacting a polyester polyol (i), an aliphatic polyfunctional isocyanate compound (ii), and an aliphatic diol (iii) having 2 to 13 carbon atoms (Method 2).
關於該方法1，具體而言可舉出：首先使脂肪族聚酯多元醇(i)與脂肪族多官能異氰酸酯化合物(ii)以當量比[(ii)中的異氰酸酯基/(i)中的羥基]達到3/1~1.1/1的比例在60~100℃的溫度條件下進行反應，將反應液的黏度達到一定的時刻作為反應終點，得到脂肪族聚酯多異氰酸酯。然後，使該脂肪族聚酯多異氰酸酯與碳原子數4~13的脂肪族二醇(iii)以當量比[該脂肪族聚酯多異氰酸酯中的異氰酸酯基/(iii)中的羥基]達到1.2/1~1.001/1的比例在60~100℃的溫度條件下進行反應的方法。The method 1 may be specifically described as follows: first, the aliphatic polyester polyol (i) and the aliphatic polyfunctional isocyanate compound (ii) are used in an equivalent ratio of the isocyanate group in ((ii) / (i) Hydroxyl] was reached at a ratio of 3/1 to 1.1 / 1, and the reaction was carried out at a temperature of 60 to 100 ° C., and the point at which the viscosity of the reaction solution reached a certain point was used as the end point of the reaction to obtain an aliphatic polyester polyisocyanate. Then, the aliphatic polyester polyisocyanate and the aliphatic diol (iii) having 4 to 13 carbon atoms were brought to an equivalent ratio [isocyanate group in the aliphatic polyester polyisocyanate / hydroxy group in (iii)] to 1.2 A method of performing a reaction at a temperature ratio of / 1 to 1.001 / 1 at a temperature of 60 to 100 ° C.
另一方面，關於該方法2，具體而言可舉出：使脂肪族聚酯多元醇(i)、脂肪族多官能異氰酸酯化合物(ii)、和碳原子數4~13的脂肪族二醇(iii)以質量比[(i)/(iii)]達到1/1~20/1的比例、並且相對於(i)中的羥基與(iii)中的羥基的合計的脂肪族多官能異氰酸酯化合物(ii)中的異氰酸酯基的當量比[((i)中的羥基+(iii)中的羥基)/(ii)中的異氰酸酯基]達到1.2/1~1.001/1的比例在60~100℃的溫度條件下進行反應的方法。On the other hand, the method 2 specifically includes an aliphatic polyester polyol (i), an aliphatic polyfunctional isocyanate compound (ii), and an aliphatic diol having 4 to 13 carbon atoms ( iii) An aliphatic polyfunctional isocyanate compound with a mass ratio [(i) / (iii)] of 1/1 to 20/1, and relative to the total of the hydroxyl groups in (i) and (iii) The equivalent ratio of isocyanate group in (ii) [(hydroxyl in (i) + hydroxyl in (iii)) / isocyanate in (ii)] reaches a ratio of 1.2 / 1 ~ 1.001 / 1 at 60 ~ 100 ° C The method of carrying out the reaction under the temperature condition.
另外，該方法1或方法2中的胺基甲酸酯化的反應可以使用胺基甲酸酯化催化劑。In the urethanization reaction in the method 1 or the method 2, a urethanization catalyst can be used.
上述的方法1和方法2中，特別是對於本發明而言，從最終得到的新穎聚酯胺基甲酸酯多元醇中起因於該碳原子數2~13的脂肪族二醇(iii)的脂肪族基團、和起因於該脂肪族聚酯多元醇(i)的聚酯結構部位隨機存在，從而能夠使該新穎聚酯胺基甲酸酯多元醇的耐濕性提高的觀點出發，宜為該方法2。In the above-mentioned methods 1 and 2, especially for the present invention, from the novel polyester urethane polyol finally obtained, it is caused by the aliphatic diol (iii) having 2 to 13 carbon atoms. From the viewpoint that the aliphatic group and the polyester structure site due to the aliphatic polyester polyol (i) are present at random, it is possible to improve the moisture resistance of the novel polyester urethane polyol. For the method 2.
這樣得到的新穎聚酯聚胺酯多元醇宜為其重均分子量(Mw)為10,000~200,000的範圍。重均分子量(Mw)處於該範圍時，硬化物顯示出高的強度，成為初始的接著強度優異的樹脂組成物，並且樹脂組成物達到適於塗佈的黏度。即，在重均分子量(Mw)小於10,000時，由於初始的接著強度下降、並且黏度低，因此成為難以均勻地塗佈的樹脂組成物。另一方面，在超過200,000時，由於黏度高，因此成為難以進行塗佈的樹脂組成物。其中，從可得到初始的接著強度高、並且濕熱條件下的基材接著性也優異的樹脂組成物的觀點出發，重均分子量(Mw)較佳為10,000~100,000的範圍。The novel polyester polyurethane polyol thus obtained preferably has a weight average molecular weight (Mw) in the range of 10,000 to 200,000. When the weight average molecular weight (Mw) is within this range, the cured product exhibits high strength, and becomes a resin composition having excellent initial adhesive strength, and the resin composition has a viscosity suitable for coating. That is, when the weight-average molecular weight (Mw) is less than 10,000, the initial adhesive strength is reduced and the viscosity is low, so that it becomes a resin composition that is difficult to apply uniformly. On the other hand, when it exceeds 200,000, since it has high viscosity, it becomes a resin composition which is difficult to apply. Among these, the weight average molecular weight (Mw) is preferably in the range of 10,000 to 100,000 from the viewpoint that a resin composition having high initial bonding strength and excellent substrate adhesion under moist heat conditions can be obtained.
另外，該新穎聚酯聚胺酯多元醇宜為分子量分佈(Mw/Mn)為2.0~15的範圍。即，藉由分子量分佈(Mw/Mn)處於該範圍內，可同時發揮出起因於低分子量成分的與基材的密合性提高的效果、和起因於高分子量成分的硬化物達到高強度的效果，因此成為濕熱條件下的基材接著性優異、初始的接著強度高的樹脂組成物。具體而言，在分子量分佈(Mw/Mn)為2.0以上時，初始的接著強度提高。其中，從可得到濕熱條件下的基材接著性更優異的樹脂組成物的觀點出發，分子量分佈(Mw/Mn)特別較佳為2.0~10.0的範圍。In addition, the novel polyester polyurethane polyol preferably has a molecular weight distribution (Mw / Mn) in a range of 2.0 to 15. That is, when the molecular weight distribution (Mw / Mn) is within this range, the effect of improving the adhesion to the substrate due to the low molecular weight component and the high strength of the hardened product due to the high molecular weight component can be simultaneously exhibited. As a result, it is a resin composition that has excellent substrate adhesion under moist heat conditions and high initial adhesion strength. Specifically, when the molecular weight distribution (Mw / Mn) is 2.0 or more, the initial bonding strength is improved. Among these, the molecular weight distribution (Mw / Mn) is particularly preferably in the range of 2.0 to 10.0 from the viewpoint that a resin composition having more excellent substrate adhesion under moist heat conditions can be obtained.
進一步，從成為濕熱條件下的基材接著性優異、且適於塗佈的黏度的樹脂組成物的觀點出發，該新穎聚酯聚胺酯多元醇的數均分子量(Mn)較佳為5,000~50,000的範圍，特別較佳為6,000~30,000的範圍。Furthermore, the number average molecular weight (Mn) of the novel polyester polyurethane polyol is preferably from 5,000 to 50,000 from the viewpoint of being a resin composition having excellent substrate adhesion under moist heat conditions and viscosity suitable for coating. The range is particularly preferably in the range of 6,000 to 30,000.
需要說明的是，本申請發明中新穎聚酯聚胺酯多元醇的重均分子量(Mw)和數均分子量(Mn)為藉由下述條件的凝膠滲透層析法(GPC)測定的值。In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the novel polyester polyurethane polyol in the present invention are values measured by gel permeation chromatography (GPC) under the following conditions.
測定裝置；東曹(股)公司製HLC-8220GPC 管柱；東曹(股)公司製TSK-GUARDCOLUMN SuperHZ-L + 東曹(股)公司製TSK-GEL SuperHZM-M×4 檢測器；RI(差示折射計) 資料處理；東曹(股)公司製multi-station GPC-8020model II 測定條件；管柱溫40℃ 溶劑；四氫呋喃 流速0.35ml/分鐘 標準；單分散聚苯乙烯 試樣；將以樹脂固體成分換算為0.2質量%的四氫呋喃溶液用微濾器過濾後的物質(100μl)Measuring device; HLC-8220GPC cymbal column manufactured by Tosoh Corporation; TSK-GUARDCOLUMN SuperHZ-L 东 manufactured by Tosoh Corporation + TSK-GEL SuperHZM-M × 4 detector manufactured by Tosoh Corporation; RI ( Differential refractometer) Data processing; multi-station GPC-8020model II made by Tosoh Corporation measurement conditions; column temperature 40 ° C solvent; tetrahydrofuran flow rate 0.35ml / min standard; monodisperse polystyrene sample; Resin solid content converted to 0.2% by mass of tetrahydrofuran solution filtered through a microfilter (100 μl)
另外，從與濕熱條件下的基材的接著性優異的觀點出發，該新穎聚酯聚胺酯多元醇的羥值較佳為2~30mg KOH/g的範圍，更佳為5~20mg KOH/g的範圍。In addition, from the viewpoint of excellent adhesion to a substrate under moist heat conditions, the hydroxyl value of the novel polyester polyurethane polyol is preferably in the range of 2 to 30 mg KOH / g, and more preferably 5 to 20 mg KOH / g. range.
以上詳述的本發明的新穎聚酯聚胺酯多元醇作為雙液型疊層接著劑的主劑即多元醇劑而有用，其能夠與硬化劑同時使用，但宜為將含有該新穎聚酯聚胺酯多元醇(以下將其表述為“聚酯聚胺酯多元醇(A)”。)、和多官能環氧化合物(B)的樹脂組成物以雙液型疊層接著劑的主劑的形式使用。即，藉由在該聚酯聚胺酯多元醇(A)的基礎上並用多官能環氧化合物(B)，由此，在接著層吸濕時該多官能環氧化合物(B)中的環氧基捕捉由於該聚酯聚胺酯多元醇(A)的水解而產生的羧基，從而能夠使該接著層的耐濕熱性進一步提高。該多官能環氧化合物(B)較佳為其數均分子量(Mn)為300~5,000的範圍的含有羥基的環氧樹脂。即，在數均分子量(Mn)為300以上時，耐濕熱性、以及與基材的接著強度變得進一步良好，另外在數均分子量(Mn)為5,000以下時，與該聚酯聚胺酯多元醇(A)的相容性變得良好。從它們的平衡優異的觀點出發，其中，更宜為數均分子量(Mn)為400~2,000的範圍。The novel polyester polyurethane polyol of the present invention detailed above is useful as a polyol agent which is a main agent of a two-liquid type laminating adhesive, and it can be used together with a hardener. However, it is preferable to polyhydride the polyester polyester containing the novel polyester polyurethane. An alcohol (hereinafter referred to as "polyester polyurethane polyol (A)") and a resin composition of the polyfunctional epoxy compound (B) are used as a main agent of a two-liquid type laminating adhesive. That is, by using a polyfunctional epoxy compound (B) in combination with the polyester polyurethane polyol (A), the epoxy group in the polyfunctional epoxy compound (B) is hygroscopic at the time of moisture absorption in the adhesive layer. By capturing the carboxyl group generated by the hydrolysis of the polyester polyurethane polyol (A), the moisture and heat resistance of the adhesive layer can be further improved. The polyfunctional epoxy compound (B) is preferably a hydroxyl group-containing epoxy resin having a number average molecular weight (Mn) in a range of 300 to 5,000. That is, when the number average molecular weight (Mn) is 300 or more, the moist heat resistance and the adhesion strength to the substrate are further improved, and when the number average molecular weight (Mn) is 5,000 or less, the polyester polyurethane polyol The compatibility of (A) becomes good. From the viewpoint of their excellent balance, the number average molecular weight (Mn) is more preferably in the range of 400 to 2,000.
另外，由於可得到硬化性更優異的樹脂組成物，該多官能環氧化合物(B)的羥值較佳為30~160mg KOH的範圍，更佳為50~150mg KOH/g的範圍。In addition, since a resin composition having more excellent curability can be obtained, the hydroxyl value of the polyfunctional epoxy compound (B) is preferably in the range of 30 to 160 mg KOH, and more preferably in the range of 50 to 150 mg KOH / g.
就該多官能環氧化合物(B)而言，例如可舉出：雙酚A型環氧樹脂、雙酚F型環氧樹脂等雙酚型環氧樹脂；聯苯型環氧樹脂、四甲基聯苯型環氧樹脂等聯苯型環氧樹脂；二環戊二烯-酚加成反應型環氧樹脂等。它們可以分別單獨使用，也可以兩種以上並用。其中，從可得到濕熱條件下的基材接著性和初始的接著強度優異的樹脂組成物的觀點出發，宜為雙酚型的環氧樹脂。Examples of the polyfunctional epoxy compound (B) include bisphenol epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin; biphenyl epoxy resin and tetramethyl Biphenyl epoxy resins such as biphenyl epoxy resins; dicyclopentadiene-phenol addition reaction epoxy resins, etc. They can be used individually or in combination of two or more kinds. Among these, a bisphenol-type epoxy resin is preferred from the viewpoint of obtaining a resin composition having excellent substrate adhesion and initial bonding strength under moist heat conditions.
進一步，該樹脂組成物藉由將該聚酯聚胺酯多元醇(A)和多官能環氧化合物(B)、以及含有羥基的脂肪族聚碳酸酯(C)並用，能夠使硬化物的交聯密度飛躍性地提高，能夠使基材接著性進一步提高。Furthermore, the resin composition can be used in combination with the polyester polyurethane polyol (A), the polyfunctional epoxy compound (B), and the aliphatic polycarbonate (C) containing a hydroxyl group to increase the crosslinking density of the cured product. This dramatically improves the adhesion of the substrate.
從羥基濃度適度提高、且硬化時的交聯密度的提高變得顯著的觀點出發，宜為在此使用的含有羥基的脂肪族聚碳酸酯(C)的數均分子量(Mn)處於5~3,000的範圍，特別宜為數均分子量(Mn)為800~2,000的範圍。需要說明的是，在此數均分子量(Mn)的測定值為藉由與該新穎聚酯聚胺酯多元醇的GPC測定條件相同的條件測定的值。From the viewpoint of a moderate increase in the hydroxyl concentration and a significant increase in the crosslinking density during curing, the number-average molecular weight (Mn) of the hydroxyl-containing aliphatic polycarbonate (C) used here is preferably 5 to 3,000. It is particularly preferable that the number average molecular weight (Mn) is in a range of 800 to 2,000. It should be noted that the measurement value of the number average molecular weight (Mn) is a value measured under the same conditions as the GPC measurement conditions of the novel polyester polyurethane polyol.
從成為硬化性更優異的樹脂組成物的觀點出發，該含有羥基的脂肪族聚碳酸酯(C)的羥值較佳為20~300mg KOH/g的範圍，特別更佳為40~250mg KOH/g的範圍。另外，從濕熱條件下的基材接著性優異的觀點出發，較佳為聚碳酸酯二醇。From the viewpoint of being a resin composition having more excellent curability, the hydroxyl value of the hydroxyl-containing aliphatic polycarbonate (C) is preferably in the range of 20 to 300 mg KOH / g, and particularly preferably 40 to 250 mg KOH / The range of g. Moreover, a polycarbonate diol is preferable at the point which is excellent in the adhesiveness of the base material under moist heat conditions.
在此，該含有羥基的聚碳酸酯(C)例如可以藉由使多元醇與羰基化劑進行縮聚反應的方法來製造。Here, the polycarbonate (C) containing a hydroxyl group can be produced, for example, by a method of subjecting a polyhydric alcohol to a polycondensation reaction with a carbonylating agent.
該含有羥基的聚碳酸酯(C)的製造中使用的多元醇例如可使用作為該新穎聚酯聚胺酯二醇的原料的支鏈烷烴多元醇(i-1)、或作為非支鏈烷烴二醇(i-2)而舉出的化合物中的任意一種。The polyol used in the production of the hydroxyl-containing polycarbonate (C) can be, for example, a branched alkane polyol (i-1) as a raw material of the novel polyester diol, or an unbranched alkane diol. (i-2) Any one of the compounds listed.
另外，就該含有羥基的聚碳酸酯(C)的製造中使用的羰基化劑而言，例如可舉出：碳酸亞乙酯、碳酸亞丙酯、碳酸二甲酯、碳酸二乙酯、碳酸二丁酯、碳酸二苯酯等。它們可以分別單獨使用，也可以兩種以上並用。Examples of the carbonylating agent used in the production of the hydroxyl-containing polycarbonate (C) include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and carbonic acid. Dibutyl ester, diphenyl carbonate, etc. They can be used individually or in combination of two or more kinds.
本發明的樹脂組成物藉由相對於該聚酯聚胺酯多元醇(A) 100質量份以該多官能環氧化合物(B)達到5~20質量份的範圍的比例、並且該聚碳酸酯樹脂(C)達到5~20質量份的範圍的比例含有該聚酯聚胺酯多元醇(A)、該多官能環氧化合物(B)、和該含有羥基的聚碳酸酯樹脂(C)，由此成為與各種基材的接著性優異、即使在濕熱條件下也能夠維持高的基材接著性的樹脂組成物，從該觀點出發為理想。The resin composition of the present invention has a ratio of the polyfunctional epoxy compound (B) in a range of 5 to 20 parts by mass relative to 100 parts by mass of the polyester polyurethane polyol (A), and the polycarbonate resin ( C) The polyester polyurethane polyol (A), the polyfunctional epoxy compound (B), and the hydroxyl-containing polycarbonate resin (C) are contained in a proportion in a range of 5 to 20 parts by mass. A resin composition having excellent adhesion to various substrates and capable of maintaining high substrate adhesion even under moist heat conditions is preferred from this viewpoint.
本發明的樹脂組成物還可以含有除該聚酯聚胺酯多元醇(A)、該多官能環氧化合物(B)、和該含有羥基的聚碳酸酯樹脂(C)以外的含有羥基的化合物。就這樣的含有羥基的化合物而言，例如可舉出：使多元酸與多元醇反應而得到的聚酯多元醇、多元酸、使多元醇和多異氰酸酯反應而得到的數均分子量(Mw)小於25,000的聚酯聚胺酯多元醇、二元酸、使二醇和二異氰酸酯反應而得到的直鏈型的聚酯聚胺酯多元醇、聚氧乙二醇、聚氧丙二醇等醚二醇、雙酚A、雙酚F等雙酚、該雙酚與環氧乙烷、環氧丙烷等加成而得到的雙酚的環氧烷加成物等。它們可以分別單獨使用，也可以兩種以上並用。The resin composition of the present invention may further contain a hydroxyl-containing compound other than the polyester polyurethane polyol (A), the polyfunctional epoxy compound (B), and the hydroxyl-containing polycarbonate resin (C). Examples of such a hydroxyl-containing compound include polyester polyols obtained by reacting a polybasic acid with a polyol, polybasic acids, and a number average molecular weight (Mw) obtained by reacting a polyol and a polyisocyanate, which are less than 25,000. Polyester polyurethane polyol, dibasic acid, linear polyester polyurethane polyol obtained by reacting a diol and a diisocyanate, ether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, bisphenol A, bisphenol A bisphenol such as F, an alkylene oxide adduct of bisphenol obtained by addition of the bisphenol to ethylene oxide, propylene oxide, or the like. They can be used individually or in combination of two or more kinds.
在本發明的樹脂組成物含有除該聚酯聚胺酯多元醇(A)、該多官能環氧化合物(B)、和該含有羥基的聚碳酸酯樹脂(C)以外的含有羥基的化合物時，由於能得到對各種基材的接著性優異、即使在濕熱條件下也能夠維持高的基材接著性的樹脂組成物，其含有量相對於該聚酯聚胺酯多元醇(A)100質量份較佳為達到5~20質量份的範圍的比例。When the resin composition of the present invention contains a hydroxyl-containing compound other than the polyester polyurethane polyol (A), the polyfunctional epoxy compound (B), and the hydroxyl-containing polycarbonate resin (C), A resin composition having excellent adhesion to various substrates and maintaining high substrate adhesion even under moist heat conditions can be obtained, and its content is preferably based on 100 parts by mass of the polyester polyurethane polyol (A). A ratio in the range of 5 to 20 parts by mass.
本發明的硬化性樹脂組成物使用含有該聚酯聚胺酯多元醇(A)的雙液型疊層接著劑用多元醇劑、或含有該(A)~(C)的各成分的樹脂組成物作為主劑，並且使用脂肪族多異氰酸酯(D)作為其硬化劑。The curable resin composition of the present invention uses a polyol agent for a two-liquid type laminate adhesive containing the polyester polyurethane polyol (A), or a resin composition containing each component of the components (A) to (C). The main agent, and an aliphatic polyisocyanate (D) is used as its hardener.
該脂肪族多異氰酸酯(D)例如可舉出作為該脂肪族多官能異氰酸酯化合物(ii)而列舉的各種多異氰酸酯。這些多異氰酸酯(D)可以一種單獨使用，也可以兩種以上並用。Examples of the aliphatic polyisocyanate (D) include various polyisocyanates listed as the aliphatic polyfunctional isocyanate compound (ii). These polyisocyanates (D) may be used individually by 1 type, and may use 2 or more types together.
這些脂肪族多異氰酸酯(D)中，在濕熱條件下的基材密合性優異方面，宜為該氰脲酸酯型多異氰酸酯化合物。Among these aliphatic polyisocyanates (D), the cyanurate-type polyisocyanate compound is preferred in terms of excellent substrate adhesion under moist heat conditions.
本發明中，由於成為硬化性更優異的硬化性樹脂組成物，就該脂肪族多異氰酸酯(D)的配合比例而言，宜為該聚酯聚胺酯多元醇(A)、該環氧化合物(B)和該含有羥基的聚碳酸酯樹脂(C)中含有的羥基的合計莫耳數[OH]、與該脂肪族多異氰酸酯(D)中含有的異氰酸酯基的莫耳數[NCO]之比[OH]/[NCO]為1/1~1/2的範圍，更佳為1/1.05~1/1.5的範圍。In the present invention, since the curable resin composition is more excellent in curability, the blend ratio of the aliphatic polyisocyanate (D) is preferably the polyester polyurethane polyol (A) and the epoxy compound (B ) And the total molar number [OH] of the hydroxyl groups contained in the hydroxyl-containing polycarbonate resin (C) and the molar number [NCO] of the isocyanate groups contained in the aliphatic polyisocyanate (D) [ OH] / [NCO] is in the range of 1/1 to 1/2, and more preferably in the range of 1 / 1.05 to 1 / 1.5.
另外，在作為主劑使用的該樹脂組成物含有除該聚酯聚胺酯多元醇(A)、該多官能環氧化合物(B)、和該含有羥基的聚碳酸酯(C)以外的含有羥基的化合物時，就該脂肪族多異氰酸酯(D)的配合比例而言，宜為該硬化性樹脂組成物中的羥基的合計莫耳數[OH]與該多異氰酸酯化合物(D)中含有的異氰酸酯基的莫耳數[NCO]之比[OH]/[NCO]為1/1~1/2的範圍，更佳為1/1.05~1/1.5的範圍。In addition, the resin composition used as a main agent contains a hydroxyl group-containing resin other than the polyester polyurethane polyol (A), the polyfunctional epoxy compound (B), and the hydroxyl group-containing polycarbonate (C). In the case of a compound, the compounding ratio of the aliphatic polyisocyanate (D) is preferably a total molar number [OH] of hydroxyl groups in the curable resin composition and an isocyanate group contained in the polyisocyanate compound (D). The molar number [NCO] ratio [OH] / [NCO] is in the range of 1/1 to 1/2, and more preferably in the range of 1 / 1.05 to 1 / 1.5.
本申請發明的硬化性樹脂組成物可以還含有各種溶劑。就該溶劑而言，例如可舉出：丙酮、甲乙酮(MEK)、甲基異丁酮等酮系化合物、四氫呋喃(THF)、二氧雜環戊烷等環狀醚系化合物、乙酸甲酯、乙酸乙酯、乙酸丁酯等酯系化合物、甲苯、二甲苯等芳香族系化合物、卡必醇、溶纖劑、甲醇、異丙醇、丁醇、丙二醇單甲醚等醇系化合物。它們可以單獨使用，也可以兩種以上並用。The curable resin composition of the present invention may further contain various solvents. Examples of the solvent include ketone compounds such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclic ether compounds such as tetrahydrofuran (THF), and dioxolane, methyl acetate, Ester-based compounds such as ethyl acetate and butyl acetate, aromatic compounds such as toluene and xylene, alcohol compounds such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. They can be used alone or in combination of two or more.
本發明的硬化性樹脂組成物可以還含有紫外線吸收劑、抗氧化劑、矽系添加劑、氟系添加劑、流變控制劑、脫泡劑、防靜電劑、防霧劑等各種添加劑。The curable resin composition of the present invention may further contain various additives such as an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, a rheology control agent, a defoaming agent, an antistatic agent, and an antifog agent.
本申請發明的硬化性樹脂組成物作為用於將各種塑膠膜接著的雙液型疊層用接著劑而有用。The curable resin composition of the present invention is useful as a two-liquid type laminating adhesive for bonding various plastic films.
關於此處貼合中使用的塑膠膜，例如可舉出包含聚碳酸酯、聚對苯二甲酸乙二醇酯、聚甲基丙烯酸甲酯、聚苯乙烯、聚酯、聚烯烴、環氧樹脂、三聚氰胺樹脂、三乙醯基纖維素樹脂、聚乙烯基醇、ABS樹脂、降冰片烯系樹脂、環狀烯烴系樹脂、聚醯亞胺樹脂、聚氟代乙烯樹脂、聚偏二氟乙烯樹脂等的膜。本申請發明的雙液型疊層用接著劑即使對於上述各種膜中特別難以進行接著的包含聚氟代乙烯樹脂、聚偏二氟乙烯樹脂的膜也顯示出高的接著性。Examples of the plastic film used for bonding here include polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polystyrene, polyester, polyolefin, and epoxy resin. , Melamine resin, triethylfluorinated cellulose resin, polyvinyl alcohol, ABS resin, norbornene resin, cyclic olefin resin, polyimide resin, polyvinyl fluoride resin, polyvinylidene fluoride resin And other films. The two-liquid type laminating adhesive of the present invention exhibits high adhesion even to a film containing a polyvinyl fluoride resin or a polyvinylidene fluoride resin, which is particularly difficult to adhere among the various films described above.
在將該各種膜之間接著時，本申請發明的雙液型疊層用接著劑的使用量較佳為2~50g/m2 的範圍。When the various films are adhered to each other, the amount of the two-liquid-type laminating adhesive used in the present invention is preferably in a range of 2 to 50 g / m 2 .
使用本申請發明的雙液型疊層用接著劑將多個膜接著而得到的層疊膜具備即使在濕熱條件下也具有高的接著性、膜之間不易剝離的特徵。因此，本申請發明的雙液型疊層用接著劑能夠宜為用於在室外等嚴酷的環境下使用的層疊膜用途，如上所述，尤其宜為作為製造太陽能電池的背板時的接著劑使用。The laminated film obtained by adhering a plurality of films using the two-liquid-type laminating adhesive of the present invention has the characteristics of having high adhesion even under moist heat conditions and being difficult to peel between films. Therefore, the two-liquid laminating adhesive of the present invention can be suitably used as a laminated film for use in harsh environments such as outdoors. As described above, it is particularly suitable as an adhesive when manufacturing a back sheet for a solar cell. use.
使用本發明的雙液型疊層用接著劑製造太陽能電池背板的方法例如可舉出如下的方法：將本發明的雙液型疊層用接著劑塗佈於塑膠膜，接著將其他塑膠基材與該硬化性樹脂組成物層重疊後，在25~80℃的溫度條件下進行硬化來得到片成形體。The method for manufacturing a solar cell back sheet using the two-liquid type laminating adhesive of the present invention includes, for example, a method in which the two-liquid type laminating adhesive of the present invention is applied to a plastic film, and then other plastic-based After the material is overlapped with the curable resin composition layer, it is cured at a temperature of 25 to 80 ° C. to obtain a sheet molded body.
在此，作為將本發明的雙液型疊層用接著劑塗佈於塑膠膜的裝置，可舉出：缺角輪型塗佈機、輥刀型塗佈機、模縫塗佈機、輥塗機、棒塗機、凹版輥式塗佈機、反轉輥式塗佈機、刮板塗佈機、凹版塗佈機、微凹版塗佈機等。另外，該雙液型疊層用接著劑對塑膠基材的塗佈量以乾燥膜厚計較佳為1~50μm左右。Here, as a device for applying the two-liquid type laminating adhesive of the present invention to a plastic film, a notch wheel type coater, a roll knife type coater, a die gap coater, and a roll are mentioned. Coater, bar coater, gravure roll coater, reverse roll coater, blade coater, gravure coater, micro gravure coater, etc. The coating amount of the two-liquid-type laminating adhesive to a plastic substrate is preferably about 1 to 50 μm in terms of dry film thickness.
上述的塑膠膜和接著劑層可以存在多層。另外，可以為在塑膠膜的表面設置金屬蒸鍍膜等氣體阻擋層、在其上塗佈該雙液型疊層用接著劑並疊層另一個塑膠膜的結構。進一步，為了提高與將太陽能電池元件密封的密封材料的接著性，可以在該太陽能電池用背板的密封材料側的表面設置易接著層。為了在易接著層的表面能夠形成凹凸、使密合性提高，該易接著層宜為包含TiO2 、SiO2 、CaCO3 、SnO2 、ZrO2 和MgCO3 等金屬微粒以及黏結劑。The plastic film and the adhesive layer described above may exist in multiple layers. In addition, a structure in which a gas barrier layer such as a metal vapor-deposited film is provided on the surface of the plastic film, and the two-liquid-type laminating adhesive is coated thereon, and another plastic film may be laminated. Furthermore, in order to improve adhesiveness with the sealing material which seals a solar cell element, the surface of the sealing material side of this solar cell back sheet may be provided with an easy adhesion layer. In order to form unevenness on the surface of the easy-adhesion layer and improve adhesion, the easy-adhesion layer is preferably composed of metal particles such as TiO 2 , SiO 2 , CaCO 3 , SnO 2 , ZrO 2, and MgCO 3 , and a binder.
另外，本申請發明的太陽能電池用背板中的接著層的厚度較佳為1以上且50μm以下的範圍、特別較佳為5~15μm的範圍。The thickness of the adhesive layer in the back sheet for a solar cell of the present invention is preferably in a range of 1 to 50 μm, and particularly preferably in a range of 5 to 15 μm.
另外，使用該太陽能電池用背板而成的太陽能電池模組可以藉由在保護玻璃板上佈設乙烯-乙酸乙烯酯樹脂(EVA)片、多個太陽能電池單元、乙烯-乙酸乙烯酯樹脂(EVA)片、本發明的背板，邊真空排氣邊加熱使EVA片熔解從而將太陽能電池元件密封來製造。此時，多個太陽能電池元件藉由內部連線串聯地接合。 在此，作為太陽能電池元件，例如可舉出：單晶矽系太陽能電池元件、多晶矽系太陽能電池元件、由單結型、或串列結構型等構成的無定型矽系太陽能電池元件、砷化鎵(GaAs)、磷化銦(InP)等III-V族化合物半導體太陽能電池元件、碲化鎘(CdTe)等II-VI族化合物半導體太陽能電池元件、銅/銦/硒系(CIS系)、銅/銦/鎵/硒系(CIGS系)、銅/銦/鎵/硒/硫系(CIGSS系)等I-III-VI族化合物半導體太陽能電池元件、色素增敏型太陽能電池元件、有機太陽能電池元件等。 【實施例】In addition, a solar cell module using the solar cell back sheet can be provided with an ethylene-vinyl acetate resin (EVA) sheet, a plurality of solar battery cells, and an ethylene-vinyl acetate resin (EVA) on a protective glass plate. ) Sheet, the back sheet of the present invention is manufactured by heating the vacuum sheet while dissolving the EVA sheet to seal the solar cell element. At this time, a plurality of solar cell elements are connected in series by internal wiring. Here, as the solar cell element, for example, a single-crystal silicon-based solar cell element, a polycrystalline silicon-based solar cell element, an amorphous silicon-based solar cell element composed of a single junction type or a tandem structure type, or the like, may be mentioned. Group III-V compound semiconductor solar cell elements such as gallium (GaAs) and indium phosphide (InP), Group II-VI compound semiconductor solar cell elements such as cadmium telluride (CdTe), copper / indium / selenium (CIS), Group I-III-VI compound semiconductor solar cell elements such as copper / indium / gallium / selenium (CIGS), copper / indium / gallium / selenium / sulfur (CIGSS), pigment-sensitized solar cell elements, organic solar cells Battery elements, etc. [Example]
以下舉出具體的合成例、實施例來詳細地說明本發明，但本發明並不限定於這些實施例。Specific synthesis examples and examples are given below to describe the present invention in detail, but the present invention is not limited to these examples.
需要說明的是，本申請實施例中，數均分子量(Mn)和重均分子量(Mw)藉由下述條件的凝膠滲透層析法(GPC)來測定。In addition, in the Example of this application, the number average molecular weight (Mn) and weight average molecular weight (Mw) are measured by the gel permeation chromatography (GPC) of the following conditions.
測定裝置；東曹(股)公司製HLC-8220GPC 管柱；東曹(股)公司製TSK-GUARDCOLUMN SuperHZ-L +東曹(股)公司製TSK-GEL SuperHZM-M×4 檢測器；RI(差示折射計) 數據處理；東曹(股)公司製multi-station GPC-8020 model II 測定條件；管柱溫40℃ 溶劑：四氫呋喃 流速：0.35ml/分鐘 標準；單分散聚苯乙烯 試樣；將以樹脂固體成分換算為0.2質量%的四氫呋喃溶液用微濾器過濾後的物質(100μl)Measuring device; HLC-8220GPC cymbal column manufactured by Tosoh Corporation; TSK-GUARDCOLUMN SuperHZ-L 东 manufactured by Tosoh Corporation + TSK-GEL SuperHZM-M × 4 detector manufactured by Tosoh Corporation; RI ( (Differential refractometer) multi data processing; multi-station GPC-8020 model II manufactured by Tosoh Corporation measurement conditions; column temperature 40 ° C solvent: tetrahydrofuran flow rate: 0.35ml / min standard; monodisperse polystyrene sample; A substance obtained by filtering a tetrahydrofuran solution having a resin solid content of 0.2% by mass through a microfilter (100 μl)
另外，就紅外線吸收光譜而言，將聚酯聚胺酯多元醇(A1)的溶液塗敷於KBr板，製作使溶劑揮發後的試樣，對其進行測定。In addition, in the infrared absorption spectrum, a solution of the polyester polyurethane polyol (A1) was applied to a KBr plate, and a sample was prepared by volatilizing the solvent, and the measurement was performed.
實施例1[聚酯聚胺酯多元醇(A1)的合成] 在具有攪拌棒、溫度感測器、精餾管的燒瓶中加入新戊二醇471.6質量份、己二酸510.5質量份和二(乙醯丙酮基)鈦酸二異丙酯(松本精細化工 (股)公司製“Orgatix TC-100”)0.6質量份，邊向燒瓶内吹入乾燥氮氣氣並進行攪拌，邊加熱至230~250℃進行酯化反應。在酸值達到2.0mg KOH/g以下的時刻停止反應，冷卻至100℃後，用乙酸乙酯將固體成分稀釋至80質量%，得到聚酯二醇的乙酸乙酯溶液。所得到的聚酯二醇的羥值為117mg KOH/g。Example 1 [Synthesis of Polyester Polyurethane Polyol (A1)] In a flask having a stir bar, a temperature sensor, and a rectification tube, 471.6 parts by mass of neopentyl glycol, 510.5 parts by mass of adipic acid, and di (ethyl醯 acetone group) 0.6 parts by mass of diisopropyl titanate ("Orgatix-100TC-100" manufactured by Matsumoto Fine Chemicals Co., Ltd.), dry nitrogen gas is blown into the flask and stirred, and heated to 230-250 ° C An esterification reaction is performed. The reaction was stopped when the acid value reached 2.0 mg KOH / g or less, and after cooling to 100 ° C, the solid content was diluted to 80% by mass with ethyl acetate to obtain an ethyl acetate solution of polyester diol. The hydroxyl value of the obtained polyester diol was 117 mg KOH / g.
接著，在該聚酯二醇的乙酸乙酯溶液(聚酯多元醇的固體成分為765.0質量份)中加入1,6-己二醇90.2質量份、異佛爾酮二異氰酸酯343.1質量份，邊向燒瓶內吹入乾燥氮氣並進行攪拌，邊加熱至70~80℃進行胺基甲酸酯化反應。在異氰酸酯含有率達到0.3%以下的時刻停止反應，得到數均分子量為11000、重均分子量為29000、分子量分佈(Mw/Mn)為2.6、且羥值為8的聚酯聚胺酯多元醇。將該聚酯聚胺酯多元醇用乙酸乙酯稀釋而得的固體成分60質量%的樹脂溶液作為聚酯聚胺酯多元醇(A1)。Next, 90.2 parts by mass of 1,6-hexanediol and 343.1 parts by mass of isophorone diisocyanate were added to the ethyl acetate solution of the polyester diol (the solid content of the polyester polyol was 765.0 parts by mass). Dry nitrogen was blown into the flask and stirred, and the carbamate reaction was performed while heating to 70 to 80 ° C. The reaction was stopped when the isocyanate content reached 0.3% or less, and a polyester polyurethane polyol having a number average molecular weight of 11,000, a weight average molecular weight of 29,000, a molecular weight distribution (Mw / Mn) of 2.6, and a hydroxyl value of 8 was obtained. A 60% by mass solid resin solution obtained by diluting the polyester polyurethane polyol with ethyl acetate was used as the polyester polyurethane polyol (A1).
實施例2[聚酯聚胺酯多元醇(A2)的合成] 在具有攪拌棒、溫度感測器、精餾管的燒瓶中加入新戊二醇428.7質量份、三羥甲基丙烷5.0質量份、己二酸464.1質量份、和二(乙醯丙酮基)鈦酸二異丙酯(松本精細化工(股)公司製“Orgatix TC-100”)0.6質量份，邊向燒瓶內吹入乾燥氮氣並進行攪拌，邊加熱至230~250℃進行酯化反應。在酸值達到2.0mg KOH/g以下的時刻停止反應，冷卻至100℃後，用乙酸乙酯將固體成分稀釋至80質量%，得到聚酯二醇的乙酸乙酯溶液。所得到的聚酯二醇的羥值為120mg KOH/g。Example 2 [Synthesis of Polyester Polyurethane Polyol (A2)] In a flask having a stir bar, a temperature sensor, and a rectification tube, 428.7 parts by mass of neopentyl glycol, 5.0 parts by mass of trimethylolpropane, and hexane were added. 464.1 parts by mass of diacid and 0.6 parts by mass of di (ethylacetonyl) diisopropyl titanate ("Orgatix TC-100" manufactured by Matsumoto Fine Chemicals Co., Ltd.), dry nitrogen gas was blown into the flask and carried out. Stir and heat to 230-250 ° C for esterification. The reaction was stopped when the acid value reached 2.0 mg KOH / g or less, and after cooling to 100 ° C, the solid content was diluted to 80% by mass with ethyl acetate to obtain an ethyl acetate solution of polyester diol. The hydroxyl value of the obtained polyester diol was 120 mg KOH / g.
接著，在該聚酯二醇的乙酸乙酯溶液(聚酯多元醇的固體成分為760.3質量份)中加入1,6-己二醇83.7質量份、異佛爾酮二異氰酸酯343.1質量份，邊向燒瓶內吹入乾燥氮氣並進行攪拌，邊加熱至70~80℃進行胺基甲酸酯化反應。在異氰酸酯含有率達到0.3質量%以下的時刻停止反應，得到數均分子量為9000、重均分子量為42000、分子量分佈(Mw/Mn)為4.7、且羥值為10的聚酯聚胺酯多元醇。將該聚酯聚胺酯多元醇用乙酸乙酯稀釋而得的固體成分60質量%的樹脂溶液作為聚酯聚胺酯多元醇(A2)。Next, 83.7 parts by mass of 1,6-hexanediol and 343.1 parts by mass of isophorone diisocyanate were added to this ethyl acetate solution of polyester diol (the solid content of the polyester polyol was 760.3 parts by mass). Dry nitrogen was blown into the flask and stirred, and the carbamate reaction was performed while heating to 70 to 80 ° C. The reaction was stopped when the isocyanate content reached 0.3% by mass or less, and a polyester polyurethane polyol having a number average molecular weight of 9000, a weight average molecular weight of 42,000, a molecular weight distribution (Mw / Mn) of 4.7, and a hydroxyl value of 10 was obtained. A resin solution having a solid content of 60% by mass of the polyester polyurethane polyol diluted with ethyl acetate was used as the polyester polyurethane polyol (A2).
比較例1[聚酯多元醇(a1)的合成] 在具有攪拌棒、溫度感測器、精餾管的燒瓶中加入新戊二醇371.0份、乙二醇556.5質量份、癸二酸927.5質量份、間苯二甲酸1298.6質量份和二(乙醯丙酮基)鈦酸二異丙酯(松本精細化工(股)公司製“Orgatix TC-100”)1.0質量份，邊向燒瓶內吹入乾燥氮氣並進行攪拌，邊加熱至230~250℃進行酯化反應。在酸值達到1.0mg KOH/g以下的時刻停止反應，冷卻至100℃後，用乙酸乙酯將固體成分稀釋至60質量%。藉由該合成方法得到數均分子量為23000、重均分子量為75000、分子量分佈(Mw/Mn)為3.3、且羥值為13mg KOH/g的聚酯多元醇。將該樹脂溶液作為聚酯多元醇(a1)。Comparative Example 1 [Synthesis of Polyester Polyol (a1)] Into a flask equipped with a stir bar, a temperature sensor, and a rectification tube, 371.0 parts of neopentyl glycol, 556.5 parts by mass of ethylene glycol, and 927.5 parts of sebacic acid were added. Parts, 1298.6 parts by mass of isophthalic acid, and 1.0 part by mass of diisopropyl di (ethylacetonyl) titanate ("OrgatixgTC-100" manufactured by Matsumoto Fine Chemicals Co., Ltd.), blown into the flask and drying Stir with nitrogen and heat to 230-250 ° C for esterification reaction. The reaction was stopped when the acid value reached 1.0 mg KOH / g or less, and after cooling to 100 ° C, the solid content was diluted to 60% by mass with ethyl acetate. A polyester polyol having a number average molecular weight of 23,000, a weight average molecular weight of 75,000, a molecular weight distribution (Mw / Mn) of 3.3, and a hydroxyl value of 13 mg KOH / g was obtained by this synthesis method. This resin solution was made into a polyester polyol (a1).
比較例2[聚酯聚胺酯多元醇(a2)的合成] 在具有攪拌棒、溫度感測器、精餾管的燒瓶中加入新戊二醇382.1份、乙二醇573.1質量份、癸二酸859.7質量份、間苯二甲酸1337.3質量份和二(乙醯丙酮基)鈦酸二異丙酯(松本精細化工(股)公司製“Orgatix TC-100”)1.0質量份，邊向燒瓶內吹入乾燥氮氣並進行攪拌，邊加熱至230~250℃進行酯化反應。在酸值達到1.0mg KOH/g以下的時刻停止反應，冷卻至100℃後，用乙酸乙酯將固體成分稀釋至80質量%。接著加入異佛爾酮二異氰酸酯129.0份，邊向燒瓶內吹入乾燥氮氣並進行攪拌，邊加熱至70~80℃進行胺基甲酸酯化反應。在異氰酸酯含有率達到0.3%以下的時刻停止反應，得到數均分子量為12000、重均分子量為37000、分子量分佈(Mw/Mn)為3.1、且羥值為14mg KOH/g的聚酯聚胺酯多元醇。將該聚酯聚胺酯多元醇用乙酸乙酯稀釋而得的固體成分60質量%的樹脂溶液作為聚酯聚胺酯多元醇(a2)。Comparative Example 2 [Synthesis of Polyester Polyurethane Polyol (a2)] Into a flask having a stir bar, a temperature sensor, and a rectification tube, 382.1 parts of neopentyl glycol, 573.1 parts by mass of ethylene glycol, and 859.7 parts of sebacic acid were added. Mass parts, 1337.3 parts by mass of isophthalic acid, and 1.0 part by mass of diisopropyl di (ethylacetonyl) titanate ("Orgatix TC-100" manufactured by Matsumoto Fine Chemicals Co., Ltd.) were blown into the flask. The nitrogen was dried and stirred, and the esterification reaction was performed while heating to 230-250 ° C. The reaction was stopped when the acid value reached 1.0 mg KOH / g or less, and after cooling to 100 ° C, the solid content was diluted to 80% by mass with ethyl acetate. Next, 129.0 parts of isophorone diisocyanate was added, and dry nitrogen was blown into the flask and stirred, and then heated to 70 to 80 ° C. to perform a urethane reaction. The reaction was stopped when the isocyanate content reached 0.3% or less, and a polyester polyurethane polyol having a number average molecular weight of 12,000, a weight average molecular weight of 37,000, a molecular weight distribution (Mw / Mn) of 3.1, and a hydroxyl value of 14 mg KOH / g was obtained. . A 60% by mass solid resin solution obtained by diluting the polyester polyurethane polyol with ethyl acetate was used as the polyester polyurethane polyol (a2).
比較例3[聚酯多元醇(a3)的合成] 在具有攪拌棒、溫度感測器、精餾管的燒瓶中加入新戊二醇514.3質量份、1,6-己二醇291.7質量份、己二酸1053.0質量份和二(乙醯丙酮基)鈦酸二異丙酯(松本精細化工(股)公司製“Orgatix TC-100”)0.8質量份，邊向燒瓶內吹入乾燥氮氣並進行攪拌，邊加熱至230~250℃進行酯化反應。在酸值達到2.0mg KOH/g以下的時刻停止反應，冷卻至100℃後，用乙酸乙酯將固體成分稀釋至60質量%。藉由該合成方法得到數均分子量為9000、重均分子量為22000、分子量分佈(Mw/Mn)為2.4、且羥值為14mg KOH/g的聚酯多元醇。將該樹脂溶液作為聚酯多元醇(a3)。Comparative Example 3 [Synthesis of Polyester Polyol (a3)] Into a flask having a stir bar, a temperature sensor, and a rectification tube, 514.3 parts by mass of neopentyl glycol, 291.7 parts by mass of 1,6-hexanediol, 1053.0 parts by mass of adipic acid and 0.8 parts by mass of di (ethylacetonyl) diisopropyl titanate ("Orgatix TC-100" manufactured by Matsumoto Fine Chemicals Co., Ltd.), dry nitrogen was blown into the flask, Stir and heat to 230-250 ° C for esterification. The reaction was stopped when the acid value reached 2.0 mg KOH / g or less, and after cooling to 100 ° C., the solid content was diluted to 60% by mass with ethyl acetate. A polyester polyol having a number average molecular weight of 9000, a weight average molecular weight of 22,000, a molecular weight distribution (Mw / Mn) of 2.4, and a hydroxyl value of 14 mg KOH / g was obtained by this synthesis method. This resin solution was used as a polyester polyol (a3).
比較例4[聚酯多元醇(a4)的合成] 在具有攪拌棒、溫度感測器、精餾管的燒瓶中加入新戊二醇560.0質量份、乙二醇400.0質量份、1,6-己二醇100.0質量份、間苯二甲酸136.0質量份、癸二酸580.0質量份、鄰苯二甲酸酐1290.0質量份和二(乙醯丙酮基)鈦酸二異丙酯(松本精細化工(股)公司製“Orgatix TC-100”)1.0質量份，邊向燒瓶內吹入乾燥氮氣並進行攪拌，邊加熱至230~250℃進行酯化反應。在酸值達到2.0mg KOH/g以下的時刻停止反應，冷卻至100℃後，用乙酸乙酯將固體成分稀釋至60質量%。藉由該合成方法得到數均分子量為14000、重均分子量為38000、分子量分佈(Mw/Mn)為2.7、且羥值為12mg KOH/g的聚酯多元醇。將該樹脂溶液作為聚酯多元醇(a4)。Comparative Example 4 [Synthesis of polyester polyol (a4)] Into a flask having a stir bar, a temperature sensor, and a distillation tube, 560.0 parts by mass of neopentyl glycol, 400.0 parts by mass of ethylene glycol, and 1,6- 100.0 parts by mass of hexanediol, 136.0 parts by mass of isophthalic acid, 580.0 parts by mass of sebacic acid, 1290.0 parts by mass of phthalic anhydride, and diisopropyl di (ethylacetonyl) titanate (Matsumoto Fine Chemicals Co., Ltd. ) 1.0 parts by mass of "Orgatix (R) TC-100" manufactured by the company), while blowing dry nitrogen into the flask and stirring, and heating to 230-250 ° C to perform an esterification reaction. The reaction was stopped when the acid value reached 2.0 mg KOH / g or less, and after cooling to 100 ° C., the solid content was diluted to 60% by mass with ethyl acetate. A polyester polyol having a number average molecular weight of 14,000, a weight average molecular weight of 38,000, a molecular weight distribution (Mw / Mn) of 2.7, and a hydroxyl value of 12 mg KOH / g was obtained by this synthesis method. This resin solution was made into a polyester polyol (a4).
實施例3~9和比較例5~7 按照表1或表2的配合組成，製備接著劑主劑，接著按照表1、表2所示的配比，將所得到的接著劑主劑和硬化劑一次性混合，製備硬化性樹脂組成物。需要說明的是，表中的主劑掺合量為固體成分質量份。硬化劑的掺合量為相對於主劑固體成分100質量份的固體成分質量。Examples 3 to 9 and Comparative Examples 5 to 7 接着 According to the mixing composition of Table 1 or Table 2, an adhesive base agent was prepared, and then the obtained adhesive base agent was hardened according to the mixing ratio shown in Table 1 and Table 2. The agents are mixed at once to prepare a curable resin composition. In addition, the mixing | blending amount of the main ingredient in a table | surface is a solid content mass part. The blending amount of the hardener is a solid content mass relative to 100 parts by mass of the solid content of the main agent.
(評價樣品的製備) 評價樣品(A)(耐變色性評價樣品) 使用30μm厚的鋁箔(東洋鋁製“A1N30H-O”)作為基材，將各實施例和比較例中得到的硬化性樹脂組成物以5~6g/m2 (乾燥質量)進行塗敷，貼合作為貼合用膜的25μm厚的氟膜(旭硝子(股)公司製“AFLEX25PW”)，得到層疊膜。將該層疊膜在50℃老化72小時後得到評價用樣品(A)。(Preparation of Evaluation Sample) Evaluation Sample (A) (Discoloration Resistance Evaluation Sample) A 30 μm-thick aluminum foil ("A1N30H-O" manufactured by Toyo Aluminum) was used as a base material, and the curable resins obtained in the respective examples and comparative examples were used. The composition was applied at 5 to 6 g / m 2 (dry mass), and a 25 μm-thick fluorine film (“AFLEX25PW” manufactured by Asahi Glass Co., Ltd.) was laminated as a laminating film to obtain a laminated film. This laminated film was aged at 50 ° C for 72 hours to obtain a sample for evaluation (A).
評價樣品(B)(耐濕熱性評價樣品) 使用125μm厚的PET膜(東麗(股)“X10S”)作為基材，將各實施例和比較例中得到的硬化性樹脂組成物以5~6g/m2 (乾燥質量)塗敷，貼合作為貼合用膜的25μm厚的氟膜(旭硝子(股)公司製“AFLEX 25PW”)，得到層疊膜。將該層疊膜在50℃老化72小時後得到評價用樣品(B)。Evaluation Sample (B) (Damp and Heat Resistance Evaluation Sample) A 125 μm-thick PET film (Toray Co., Ltd. “X10S”) was used as a base material, and the curable resin composition obtained in each of the examples and comparative examples was 5 to 6 g / m 2 (dry mass) was applied, and a 25 μm-thick fluorine film (“AFLEX 25PW” manufactured by Asahi Glass Co., Ltd.) was laminated as a film for bonding to obtain a laminated film. This laminated film was aged at 50 ° C for 72 hours to obtain a sample for evaluation (B).
(評價樣品(A)的評價方法：耐變色性) 使用拉伸試驗機(島津公司製“AGS500NG”)將該評價樣品(B)在剝離速度 300mm/min、N/15mm的條件下進行T型剝離試驗，對其初始的接著強度進行評價。對相對於該初始的接著強度的從氟膜側照射100mW/cm2 的紫外線100小時後的接著力的保持率、和塗膜的黃變性進行評價。(Evaluation method of evaluation sample (A): resistance to discoloration) Using a tensile tester ("AGS500NG" manufactured by Shimadzu Corporation), this evaluation sample (B) was T-shaped under conditions of a peeling speed of 300 mm / min and N / 15 mm. The peeling test evaluated the initial adhesive strength. The retention rate of the adhesive force after 100 hours of irradiation with 100 mW / cm 2 of ultraviolet rays from the fluorine film side and the yellowing of the coating film with respect to the initial adhesive strength were evaluated.
(評價樣品(B)的評價方法：耐濕熱性) 使用拉伸試驗機(島津公司製“AGS500NG”)將該評價樣品(A)在剝離速度300mm/min、N/15mm的條件下進行T型剝離試驗，將其強度作為接著力進行評價。對評價樣品(A)的初始的接著力、和在121℃、濕度100%環境下曝露25小時、50小時、75小時後的各自的樣品的接著力進行測定。(Evaluation method of evaluation sample (B): humidity and heat resistance) The evaluation sample (A) was subjected to a T-shape under conditions of a peeling speed of 300 mm / min and N / 15 mm using a tensile tester ("AGS500NG" manufactured by Shimadzu Corporation). In the peel test, the strength was evaluated as an adhesive force. The initial adhesive force of the evaluation sample (A) and the adhesive force of each sample after being exposed to 121 ° C and 100% humidity for 25 hours, 50 hours, and 75 hours were measured.
本發明的實施例和比較例中使用的環氧樹脂(B)如下所述。 ･環氧樹脂(B1)：氫化雙酚A環氧樹脂(三菱化學公司製“YX8034”、分子量約470) ･環氧樹脂(B2)：數均分子量(Mn)470、環氧當量245g/eq、羥值54mg KOH/g的雙酚A型環氧樹脂(DIC(股)公司製“Epiclon 860”) ･聚碳酸酯樹脂(C)：數均分子量(Mn)1,000、羥值110mg KOH/g的聚碳酸酯二醇(大賽璐化學公司製“PLACCEL CD210”) ･硬化劑(D)：六亞甲基二異氰酸酯的氰脲酸酯改性體(住友拜耳聚胺酯公司製“Sumidur N3300”)The epoxy resin (B) used in the Example of this invention and a comparative example is as follows. ･ Epoxy resin (B1): hydrogenated bisphenol A epoxy resin ("YX8034" manufactured by Mitsubishi Chemical Corporation, molecular weight of about 470) ･ Epoxy resin (B2): number average molecular weight (Mn) 470, epoxy equivalent 245g / eq Bisphenol A epoxy resin with a hydroxyl value of 54 mg KOH / g ("Epiclon 860" manufactured by DIC Corporation) ･ Polycarbonate resin (C): Number average molecular weight (Mn) 1,000, hydroxyl value of 110 mg KOH / g Polycarbonate diol ("PLACCEL CD210" manufactured by Daicel Chemical Co., Ltd.) Rhenium hardener (D): Hexamethylene diisocyanate modified cyanurate ("Sumidur N3300" manufactured by Sumitomo Bayer Polyurethanes)
需要說明的是，上述環氧樹脂(B2)的羥值是藉由GPC測定存在於該環氧樹脂(B2)中的聚合度不同的環氧樹脂的存在比例，並從該存在比例、和各聚合度的環氧樹脂的理論羥值的值計算出的值。It should be noted that the hydroxyl value of the epoxy resin (B2) is measured by GPC, and the proportion of the epoxy resins having different degrees of polymerization existing in the epoxy resin (B2) is measured. The calculated value of the theoretical hydroxyl value of the degree of polymerization of the epoxy resin.
圖 1 為實施例1中得到的聚酯聚胺酯多元醇(A1)的GPC譜圖。 圖2為實施例1中得到的聚酯聚胺酯多元醇(A1)的紅外線吸收譜圖。FIG. 1 is a GPC spectrum of the polyester polyurethane polyol (A1) obtained in Example 1. FIG. FIG. 2 is an infrared absorption spectrum of the polyester polyurethane polyol (A1) obtained in Example 1. FIG.
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| WO2018047672A1 (en) * | 2016-09-06 | 2018-03-15 | Dic株式会社 | Adhesive, blister pack laminate and blister pack using same |
| CN106520049A (en) * | 2016-10-13 | 2017-03-22 | 苏州长业材料技术有限公司 | Polyester adhesive, and preparation method and application thereof on solar energy back plate |
| JP6566147B2 (en) * | 2016-12-20 | 2019-08-28 | Dic株式会社 | Polyester polyol, reactive adhesive, and laminate |
| CN111902512B (en) * | 2018-03-28 | 2022-09-13 | Dic株式会社 | Reactive adhesive, laminated film, and package |
| CN109293904A (en) * | 2018-09-03 | 2019-02-01 | 杭州福斯特应用材料股份有限公司 | A kind of high-weatherability polyester resin and purposes |
| JP6888161B1 (en) * | 2020-10-02 | 2021-06-16 | 大日精化工業株式会社 | Urethane prepolymers, moisture-curable urethane hot-melt resin compositions, and laminates. |
| EP4321586A1 (en) * | 2021-04-08 | 2024-02-14 | ThreeBond Co., Ltd. | Two-part curable resin composition and cured product thereof |
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| CN115679702B (en) * | 2022-10-18 | 2023-09-12 | 广东裕田霸力科技股份有限公司 | Yellowing-resistant fly-weaving treating agent and preparation method thereof |
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