TWI674277B - (meth) acryloyloxy group-containing polymer - Google Patents
(meth) acryloyloxy group-containing polymer Download PDFInfo
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Abstract
本發明之目的在於,提供一種可加快組成物之硬化速度之含(甲基)丙烯醯氧基之聚合物。本發明之含(甲基)丙烯醯氧基之聚合物,其中,作為主鏈之骨架,具有由包含選自由丁二烯及異戊二烯所組成之群中至少1種的單體形成之聚合物或其氫化物,並且於至少一個末端具有以下述式(1)表示之官能基(式中,R1、R2分別單獨表示氫原子或甲基,m、n分別單獨表示1~5,*表示與前述主鏈之鍵結位置)之含(甲基)丙烯醯氧基之聚合物。 An object of the present invention is to provide a (meth) acryloxy group-containing polymer which can accelerate the hardening speed of a composition. The (meth) acryloxy group-containing polymer according to the present invention, wherein the backbone of the (meth) acryloxy group has a monomer composed of at least one monomer selected from the group consisting of butadiene and isoprene. A polymer or a hydride thereof, and having a functional group represented by the following formula (1) at least one terminal (wherein R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and m and n each independently represent 1 to 5 , * Indicates the (meth) acrylic fluorenyl group-containing polymer of the bonding position with the aforementioned main chain).
Description
本發明係關於一種含(甲基)丙烯醯氧基之聚合物。 The present invention relates to a polymer containing (meth) acrylic acid.
近年來,作為電子材料之接著劑或黏著劑,含有光聚合性樹脂之組成物為人熟知。 In recent years, a composition containing a photopolymerizable resin is known as an adhesive or an adhesive for electronic materials.
例如,專利文獻1中記載有一種光硬化性透明黏著薄膜用組成物(請求項1),其含(A)重均分子量為1萬~30萬之含(甲基)丙烯醯基之聚烯烴化合物、(B)具有羥基之(甲基)丙烯酸酯、(C)具有羥基之(甲基)丙烯酸酯以外之光聚合性單體、以及(D)光聚合引發劑,其特徵在於,(A)重均分子量為1萬~30萬之含(甲基)丙烯醯基聚烯烴之化合物係藉由使聚烯烴多元醇與多官能異氰酸酯化合物發生反應,接著相對於殘存之羥基或異氰酸酯基,使50~80mol%之具有(甲基)丙烯醯基之化合物發生反應,從而使(甲基)丙烯醯基導入分子中獲得之(甲基)丙烯酸胺基甲酸酯化合物,相對於(C)具有羥基之(甲基)丙烯酸酯以外之光 聚合性單體之總量,(C)具有羥基之(甲基)丙烯酸酯以外之光聚合性單體中包含之含羧基單體為0.1質量%以下。此外,專利文獻1之實施例2中記載有一種組成物,其含:使異佛爾酮二異氰酸酯1莫耳及氫化末端羥基聚丁二烯2莫耳發生反應,於殘存異氰酸酯基為0.1%以下時,使2-異氰酸酯丙烯酸乙酯1.4莫耳發生反應後獲得之含(甲基)丙烯醯基之聚烯烴化合物(A-2)、丙烯酸羥乙酯、丙烯酸環己酯、光聚合引發劑等。 For example, Patent Document 1 describes a composition for a photocurable transparent adhesive film (claim 1), which contains (A) a polyolefin having a (meth) acrylfluorene group having a weight average molecular weight of 10,000 to 300,000. A compound, (B) a (meth) acrylate having a hydroxyl group, (C) a photopolymerizable monomer other than the (meth) acrylate having a hydroxyl group, and (D) a photopolymerization initiator, wherein (A) The (meth) acrylfluorene-containing polyolefin having a weight average molecular weight of 10,000 to 300,000 is obtained by reacting a polyolefin polyol with a polyfunctional isocyanate compound, and then reacting the remaining hydroxyl or isocyanate groups with 50 to 80 mol% of the compound having a (meth) acrylfluorenyl group reacts, so that the (meth) acrylic acid urethane compound obtained by introducing the (meth) acrylfluorenyl group into the molecule is Light other than hydroxyl (meth) acrylate The total amount of the polymerizable monomers is 0.1% by mass or less of the carboxyl group-containing monomer contained in the photopolymerizable monomer other than the (C) acrylate having a hydroxyl group. In addition, Example 2 of Patent Document 1 describes a composition containing a reaction of 1 mole of isophorone diisocyanate and 2 moles of hydrogenated terminal hydroxy polybutadiene, and the residual isocyanate group is 0.1%. In the following, the (meth) acrylfluorenyl-containing polyolefin compound (A-2), hydroxyethyl acrylate, cyclohexyl acrylate, and a photopolymerization initiator obtained after the reaction of 1.4 mol of 2-isocyanate ethyl acrylate Wait.
[專利文獻1]國際公開第2012/043550號 [Patent Document 1] International Publication No. 2012/043550
其中,本發明者等已知曉依據專利文獻1製備含有含(甲基)丙烯醯基之聚烯烴化合物之組成物時,此種組成物之硬化速度有時會變慢。 Among them, the present inventors have known that when a composition containing a (meth) acrylfluorene-containing polyolefin compound is prepared in accordance with Patent Document 1, the hardening speed of such a composition may be slowed down.
於是,本發明之課題在於提供一種可加快組成物之硬化速度之含(甲基)丙烯醯氧基之聚合物。 Therefore, an object of the present invention is to provide a (meth) acrylic fluorenyl group-containing polymer which can accelerate the hardening speed of a composition.
本發明者等為解決上述課題深入研究後發現:作為主鏈之骨架具有由包含選自由丁二烯及異戊二烯所組成之群中至少1種的單體形成之聚合物或其氫化物, 並且於末端具有具備2個(甲基)丙烯醯氧基之特定官能基之含(甲基)丙烯醯氧基之聚合物,可加快組成物之硬化速度,而完成本發明。 The present inventors have intensively studied in order to solve the above problems, and found that the backbone as a backbone has a polymer or a hydride formed of at least one monomer selected from the group consisting of butadiene and isoprene. , In addition, a (meth) acrylic acid group-containing polymer having a specific functional group having two (meth) acrylic acid groups at the terminal can accelerate the hardening speed of the composition and complete the present invention.
即,本發明者發現,藉由以下構成可解決上述課題。 That is, the present inventors have found that the above problems can be solved by the following configuration.
1.一種含(甲基)丙烯醯氧基之聚合物,其中,作為主鏈之骨架,具有由包含選自由丁二烯及異戊二烯所組成之群中至少1種的單體形成之聚合物或其氫化物,
並且於末端具有以下述式(1)表示之官能基,
式(1)中,R1、R2分別單獨表示氫原子或甲基,m、n分別單獨表示1~5,*表示與前述主鏈之鍵結位置。 In formula (1), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, m and n each independently represent 1 to 5, and * represents a bonding position with the aforementioned main chain.
2.如請求項1之含(甲基)丙烯醯氧基之聚合物,其中,前述主鏈與前述官能基直接或透過雜原子或有機基進行鍵結。 2. The (meth) acryloxy group-containing polymer according to claim 1, wherein the main chain and the functional group are bonded directly or through a hetero atom or an organic group.
3.如請求項2之含(甲基)丙烯醯氧基之聚合物,其中,前述有機基具有2個以上之胺基甲酸酯鍵。 3. The (meth) acrylic fluorenyl group-containing polymer according to claim 2, wherein the organic group has two or more urethane bonds.
4.如請求項1至3中任一項之含(甲基)丙烯醯氧基之聚合物,其中,前述骨架具有選自由以下述式(Ia)~式(Ic)表示之重複單元所組成之群中至少1種,
式(Ia)~式(Ic)中,虛線與實線之雙重線表示單鍵或雙鍵。 In the formulae (Ia) to (Ic), the double line of the dashed line and the solid line represents a single bond or a double bond.
5.如請求項4之含(甲基)丙烯醯氧基之聚合物,其中,相對於以前述式(Ia)~式(Ic)所表示之重複單元之合計,以前述式(Ia)所表示之重複單元之含量1為0~40莫耳%, 相對於以前述式(Ia)~式(Ic)所表示之重複單元之合計,以前述式(Ib)所表示之重複單元之含量2為0~100莫耳%, 相對於以前述式(Ia)~式(Ic)所表示之重複單元之合計,以前述式(Ic)所表示之重複單元之含量3為0~100莫耳%。 5. The (meth) acrylic fluorenyl group-containing polymer according to claim 4, wherein the total of the repeating units represented by the aforementioned formulae (Ia) to (Ic) is represented by the aforementioned formula (Ia) The content of the repeating unit 1 is 0 ~ 40 mole%, With respect to the total of the repeating units represented by the aforementioned formulae (Ia) to (Ic), the content 2 of the repeating units represented by the aforementioned formula (Ib) is 0 to 100 mole%, The content of the repeating unit 3 represented by the aforementioned formula (Ic) is 0 to 100 mol% relative to the total of the repeating units represented by the aforementioned formulas (Ia) to (Ic).
6.如請求項1至5中任一項之含(甲基)丙烯醯氧基之聚合物,其中,1分子中具有3個以上之(甲基)丙烯醯氧基。 6. The (meth) propenyloxy group-containing polymer according to any one of claims 1 to 5, which has 3 or more (meth) propenyloxy groups in one molecule.
根據本發明,能夠提供一種可加快組成物之硬化速度之含(甲基)丙烯醯氧基之聚合物。 According to the present invention, it is possible to provide a (meth) acryloxy group-containing polymer which can accelerate the hardening speed of a composition.
以下,詳細說明本發明。 Hereinafter, the present invention will be described in detail.
再者,本說明書中(甲基)丙烯酸酯表示丙烯酸酯或甲基丙烯酸酯,(甲基)丙烯醯表示丙烯醯或甲基丙烯醯,(甲基)丙烯酸表示丙烯酸或甲基丙烯酸。 In addition, in this specification, (meth) acrylate means an acrylate or a methacrylate, (meth) acrylic 醯 means acryl 醯 or methacryl 醯, and (meth) acrylic acid means acrylic acid or methacrylic acid.
此外,本說明書中使用「~」表示之數值範圍意味記載於「~」前後之數值作為下限值及上限值包含的範圍。 In addition, the numerical range indicated by "~" in this specification means the range in which the numerical value described before and after "~" is included as a lower limit and an upper limit.
此外,本說明書中,成分包含2種以上之物質時,上述成分之含量係指2種以上之物質之總含量。 In addition, in this specification, when a component contains two or more substances, the content of the said component means the total content of two or more substances.
本發明之含(甲基)丙烯醯氧基之聚合物(本發明之聚合物)中,係作為主鏈之骨架具有由包含選自由丁二烯及異戊二烯所組成之群中至少1種的單體形成之聚合物或其氫化物,並且於末端具有下述式(1)表示之官能基之含(甲基)丙烯醯氧基之聚合物,
式(1)中,R1、R2分別獨立表示氫原子或甲基,m、n分別獨立表示1~5,*表示與前述主鏈之鍵結位置。 In the formula (1), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, m and n each independently represent 1 to 5, and * represents a bonding position with the aforementioned main chain.
本發明之聚合物具有如此結構,因此可認為其能夠獲得所期望之效果。雖然其原因尚未清楚,但可大致推測如下。 Since the polymer of the present invention has such a structure, it is considered that it can obtain a desired effect. Although the reason is not clear, it can be roughly estimated as follows.
即,推測位於本發明之聚合物之末端的官能基具有2個(甲基)丙烯醯氧基,因此較其反應性高,並且於末端具有1個(甲基)丙烯醯氧基之聚合物之硬化速度快。 That is, it is presumed that the functional group located at the terminal of the polymer of the present invention has two (meth) acrylic fluorenyloxy groups, and is therefore more reactive than the polymer having one (meth) acryl fluorenyloxy group at the terminal It hardens quickly.
此外,推測藉由如此反應性高,含有本發明之聚合物之組成物係接著強度優異(尤其是高溫高溼條件下之接著強度)。 In addition, it is presumed that the composition having the polymer of the present invention is excellent in adhesion strength (especially adhesion strength under high temperature and high humidity conditions) due to such high reactivity.
以下,詳細說明本發明之聚合物。 Hereinafter, the polymer of the present invention will be described in detail.
本發明之聚合物係作為其主鏈之骨架具有由包含選自由丁二烯及異戊二烯所組成之群中至少1種之單體形成之聚合物或其氫化物。 The polymer of the present invention has, as a backbone of the main chain thereof, a polymer or a hydride formed of the polymer including at least one monomer selected from the group consisting of butadiene and isoprene.
上述主鏈可為均聚物、共聚物中任一種。主鏈為共聚物時,作為上述共聚物,例如可列舉無規共聚物、嵌段共聚物、接枝共聚物、該等之組合。作為聚合物,例如可列 舉聚丁二烯、聚異戊二烯、丁二烯異戊二烯共聚物。 The main chain may be any of a homopolymer and a copolymer. When the main chain is a copolymer, examples of the copolymer include random copolymers, block copolymers, graft copolymers, and combinations thereof. As a polymer, for example Examples include polybutadiene, polyisoprene, and butadiene isoprene copolymer.
此外,上述主鏈亦可為由上述單體形成之聚合物之氫化物。上述氫化物可為使上述聚合物具有之部分或全部雙鍵氫化者。上述聚合物之加氫率並無特別限制。 In addition, the main chain may be a hydride of a polymer formed from the monomers. The hydride may be one in which some or all of the double bonds possessed by the polymer are hydrogenated. The hydrogenation rate of the polymer is not particularly limited.
本發明之聚合物之主鏈之骨架較佳具有選自由以下述式(Ia)~式(Ic)所表示之重複單元所組成之群中至少1種,
(式(Ia)~式(Ic)中,虛線與實線之雙重線表示單鍵或雙鍵。) (In the formulae (Ia) to (Ic), the double line of the dashed line and the solid line represents a single bond or a double bond.)
相對於以上述式(Ia)~式(Ic)所表示之重複單元之合計,以上述式(Ia)所表示之重複單元之含量1較佳為0~40莫耳%,更佳為0~35莫耳%。 The content of the repeating unit 1 represented by the formula (Ia) 1 is preferably 0 to 40 mole%, and more preferably 0 to the total of the repeating units represented by the formulae (Ia) to (Ic). 35 mole%.
相對於以上述式(Ia)~式(Ic)所表示之重複單元之合計,以上述式(Ib)所表示之重複單元之含量2較佳為0~100莫耳%,更佳為0~90莫耳%。 The content of the repeating unit 2 represented by the above formula (Ib) is preferably 0 to 100 mole%, and more preferably 0 to the total of the repeating units represented by the above formulas (Ia) to (Ic). 90 mol%.
相對於以上述式(Ia)~式(Ic)所表示之重複單元之合計,以上述式(Ic)所表示之重複單元之含量3較佳為 0~100莫耳%,更佳為0~50莫耳%。 The content 3 of the repeating unit represented by the above formula (Ic) is preferably relative to the total of the repeating units represented by the above formulas (Ia) to (Ic). 0 to 100 mole%, more preferably 0 to 50 mole%.
作為以式(Ia)~式(Ic)所表示之重複單元之組合,例如可列舉式(1a)與式(1b)所表示之重複單元之組合作為較佳態樣之一。 As a combination of the repeating units represented by the formula (Ia) to the formula (Ic), for example, a combination of the repeating units represented by the formula (1a) and the formula (1b) can be cited as one of the preferable aspects.
再者,本發明之聚合物之主鏈之骨架具有選自由以式(Ia)~式(Ic)所表示之重複單元所組成之群中之至少1種時,除掉含量1~3不可全部同時為0。 In addition, when the backbone of the main chain of the polymer of the present invention has at least one selected from the group consisting of repeating units represented by formula (Ia) to formula (Ic), the content of 1-3 may not be all. Also 0.
此外,可將製造本發明之聚合物時使用之原料聚合物具有之以式(Ia)~式(Ic)所表示之重複單元之各比例反映至上述含量1、2以及3中。 In addition, the respective ratios of the repeating units represented by the formula (Ia) to the formula (Ic) in the base polymer used in the production of the polymer of the present invention can be reflected to the above-mentioned contents 1, 2, and 3.
上述含量1、2以及3可根據1H-NMR(nuclear magnetic resonance:核磁共振)及13C-NMR分析之結果計算得出。 The above contents 1, 2 and 3 can be calculated from the results of 1 H-NMR (nuclear magnetic resonance) and 13 C-NMR analysis.
本發明之聚合物係於其末端具有以下述式(1)所表示之官能基。 The polymer of the present invention has a functional group represented by the following formula (1) at its terminal.
式(1)中,R1、R2分別獨立表示氫原子或甲基,m、n分別獨立表示1~5,*表示與前述主鏈之鍵結位置。 In the formula (1), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, m and n each independently represent 1 to 5, and * represents a bonding position with the aforementioned main chain.
式(1)中,m較佳為1~3。 In formula (1), m is preferably 1 to 3.
N較佳為1~3。 N is preferably 1 to 3.
R1、R2可相同亦可不同。 R 1 and R 2 may be the same or different.
作為以式(1)所示之官能基,例如可列舉下述式(1')所示之官能基, Examples of the functional group represented by the formula (1) include a functional group represented by the following formula (1 ').
式(1')中,R11、R12、m1、n1、*分別與上述式(1)之R1、R2、m、n、*相同。 In the formula (1 ′), R 11 , R 12 , m1, n1, and * are the same as R 1 , R 2 , m, n, and * in the formula (1), respectively.
再者,式(1')中與*鄰接之氧原子亦可形成具有氧原子之鍵(例如胺基甲酸酯鍵)之一部分。具有氧原子之鍵結亦可包含於下述有機基中。 Furthermore, the oxygen atom adjacent to * in the formula (1 ′) may form a part of a bond having an oxygen atom (for example, a urethane bond). The bond having an oxygen atom may be included in the organic group described below.
本發明之聚合物於1分子中具有之以式(1)所示之官能基之數量為1個或2個以上。上述官能基之數量可為10個以下。上述官能基之數量較佳為1個或2個。 The polymer of the present invention has one or more functional groups represented by formula (1) in one molecule. The number of the functional groups may be 10 or less. The number of the functional groups is preferably one or two.
本發明之聚合物可於至少1個末端或所有末端具有以式(1)所示之官能基。上述主鏈為直鏈狀時,主鏈之一末端或兩末端可具有以式(1)所示之官能基。 The polymer of the present invention may have a functional group represented by formula (1) at at least one terminal or at all terminals. When the main chain is linear, one or both ends of the main chain may have a functional group represented by formula (1).
本發明之聚合物中,上述主鏈與上述官能基可直接或透過雜原子或有機基進行鍵結。 In the polymer of the present invention, the main chain and the functional group may be bonded directly or through a hetero atom or an organic group.
(雜原子) (Heteroatom)
雜原子至少為2價即可。作為2價之雜原子,例如可列舉氧原子、氮原子、硫原子。 The hetero atom may be at least divalent. Examples of the divalent hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.
鍵結上述主鏈與上述官能基之有機基並無特別限制。例如可列舉亦可具有雜原子之烴基。再者,有機基可為2價以上。 The organic group which bonds the said main chain and the said functional group is not specifically limited. For example, a hydrocarbon group which may have a hetero atom is mentioned. The organic group may be divalent or more.
作為烴基,可列舉脂肪族烴基(包含脂環式)、芳香族烴基、該等之組合。烴基可為直鏈狀、支鏈狀以及環狀中任一者。烴基可具有不飽和鍵。 Examples of the hydrocarbon group include an aliphatic hydrocarbon group (including an alicyclic type), an aromatic hydrocarbon group, and a combination thereof. The hydrocarbon group may be any of linear, branched, and cyclic. The hydrocarbyl group may have an unsaturated bond.
作為烴基,例如可列舉甲基、乙基、六亞甲基等碳原子數1~10之烷基之殘基;環己烷等脂環式烴基之殘基:苯等芳香族烴基之殘基;來自異佛爾酮二異氰酸酯等之烷基與脂環式烴基之組合之殘基。 Examples of the hydrocarbon group include residues of alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, and hexamethylene; residues of alicyclic hydrocarbon groups such as cyclohexane: residues of aromatic hydrocarbon groups such as benzene ; Residue derived from a combination of an alkyl group of an isophorone diisocyanate and an alicyclic hydrocarbon group.
作為雜原子,例如可列舉氧原子、氮原子、硫原子、鹵素、該等之組合。 Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen, and a combination thereof.
作為組合有雜原子之取代基,例如可列舉胺基甲酸酯鍵、酯鍵、脲鍵。其中,作為較佳方式之一,可列舉胺基甲酸酯鍵。 Examples of the hetero atom-containing substituent include a urethane bond, an ester bond, and a urea bond. Among these, as one of the preferable aspects, a urethane bond is mentioned.
具有1個有機基之上述取代基之數量可為1個或2個以上。作為較佳方式之一,上述數量可列舉為2個。 The number of the above-mentioned substituents having one organic group may be one or two or more. As one of the preferred embodiments, the number may be two.
1個有機基所具有之上述取代基之數量為2個時,於2個取代基之間可配置亦可具有雜原子之烴基。此 時,有機基例如可以下述式(6)表示。 When the number of the above-mentioned substituents which one organic group has is 2, a hydrocarbon group which may have a hetero atom may be arranged between the two substituents. this In this case, the organic group can be represented by the following formula (6), for example.
式(6):亦可具有-取代基61-雜原子之烴基-取代基62- Formula (6): Hydrocarbyl-substituent 62 -which may have -substituent 61 -heteroatom
式(6)中,取代基61、取代基62可相同亦可不同,為組合有上述雜原子之取代基。 In the formula (6), the substituent 61 and the substituent 62 may be the same or different, and are a substituent in which the above hetero atom is combined.
再者,式(6)中之「-」表示鍵結(以下相同)。 In addition, "-" in Formula (6) represents a bond (the same applies hereinafter).
本發明之聚合物於1分子中所具有之(甲基)丙烯醯氧基之數量較佳為2個以上,更佳為3~6個,特佳為4個。其中,至少2個之(甲基)丙烯醯氧基來自以上述式(1)所示之官能基。 The number of (meth) acrylic fluorenyloxy groups contained in one molecule of the polymer of the present invention is preferably two or more, more preferably three to six, and particularly preferably four. Among them, at least two (meth) acrylfluorenyl groups are derived from the functional group represented by the above formula (1).
本發明之聚合物更進一步可具有與上述官能基不同之具有(甲基)丙烯醯氧基之基(以下有時會稱為「其他基」)。 The polymer of the present invention may further have a group having a (meth) acrylfluorenyl group (hereinafter sometimes referred to as "other group") different from the functional group described above.
上述其他基之鍵結位置並無特別限制,但例如可列舉本發明之聚合物之末端。 The bonding position of the other groups is not particularly limited, but examples include the terminal of the polymer of the present invention.
作為上述其他基,例如可列舉以下述式(7)所表示之基。 Examples of the other groups include a group represented by the following formula (7).
式(7):CH2=CR72-CO-O-R71-* Equation (7): CH 2 = CR 72 -CO-OR 71- *
式(7)中,R72為氫原子或甲基,R71為烴基,*表示與主鏈之鍵結位置。 In the formula (7), R 72 is a hydrogen atom or a methyl group, R 71 is a hydrocarbon group, and * represents a bonding position with the main chain.
作為R71所表示之烴基,可列舉脂肪族烴基(包含脂環式)、芳香族烴基、該等之組合。烴基可為直鏈狀、支鏈狀以及環狀中任一者。烴基可具有不飽和鍵。作為烴基,具體而言例如可列舉碳原子數1~10之亞烷基,具體而言例如可列舉亞甲基、亞乙基、三亞甲基、丁 烯基。 Examples of the hydrocarbon group represented by R 71 include an aliphatic hydrocarbon group (including an alicyclic type), an aromatic hydrocarbon group, and a combination thereof. The hydrocarbon group may be any of linear, branched, and cyclic. The hydrocarbyl group may have an unsaturated bond. Specific examples of the hydrocarbon group include an alkylene group having 1 to 10 carbon atoms, and specific examples include a methylene group, an ethylene group, a trimethylene group, and a butenyl group.
本發明之聚合物於1分子中可具有之上述其他基之數量可為0個或1個以上。上述其他基之數量可為10個以下。上述其他基之數量較佳為1個或2個。 The polymer of the present invention may have 0 or more of the above-mentioned other groups in one molecule. The number of the other bases may be 10 or less. The number of the other bases is preferably one or two.
上述其他(甲基)丙烯醯氧基可直接或透過雜原子或有機基與主鏈進行鍵結。雜原子、有機基與上述相同。 The other (meth) acrylfluorenyl groups may be bonded to the main chain directly or through a hetero atom or an organic group. Heteroatoms and organic groups are the same as described above.
作為本發明之聚合物,例如可列舉下述以式(4)所表示之聚合物。 Examples of the polymer of the present invention include a polymer represented by the following formula (4).
式(4):〔亦可具有官能基41-取代基41-雜原子之烴基-取代基42〕2-主鏈 Formula (4): [may also have functional group 41 -substituent 41 -heteroatom hydrocarbon group-substituent 42 ] 2 -main chain
式(4)中,官能基41表示以式(1)所表示之官能基或上述其他基,2個官能基41中至少1個官能基為以式(1)所表示之官能基。亦可具有以式(1)所表示之官能基、其他基、雜原子之烴基與上述相同。 In the formula (4), the functional group 41 represents a functional group represented by the formula (1) or the other group, and at least one of the two functional groups 41 is a functional group represented by the formula (1). The functional group represented by formula (1), other groups, and a hydrocarbon group having a hetero atom may be the same as those described above.
式(4)中,取代基41、取代基42與上述取代基61、取代基62相同。 In the formula (4), the substituent 41 and the substituent 42 are the same as the substituent 61 and the substituent 62 described above.
式(4)中,「取代基41-可具有雜原子之烴基-取代基42」相當於有機基。 In the formula (4), "the substituent 41 -a hydrocarbon group which may have a hetero atom-the substituent 42 " corresponds to an organic group.
本發明之聚合物之數平均分子量較佳為5,000~100,000,更佳為10,000~70,000。本發明之聚合物之數平均分子量係以四氫呋喃為溶劑,藉由聚苯乙烯換算,利用凝膠滲透層析法(GPC)測定而求得之值。 The number average molecular weight of the polymer of the present invention is preferably 5,000 to 100,000, and more preferably 10,000 to 70,000. The number-average molecular weight of the polymer of the present invention is a value obtained by measuring with a gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene.
本發明之聚合物可分別單獨或者組合兩種以上使用。 The polymer of the present invention can be used alone or in combination of two or more kinds.
本發明之聚合物可列舉具有光聚合性者作為較佳態樣之一。 The polymer of the present invention may be one having a photopolymerizable property as a preferable aspect.
使本發明之聚合物進行聚合之光並無特別限制。例如,可列舉紫外線。 The light for polymerizing the polymer of the present invention is not particularly limited. Examples include ultraviolet rays.
藉由使具有以式(1)所表示之官能基之(甲基)丙烯醯氧基發生反應,可使本發明之聚合物進行聚合。 The polymer of the present invention can be polymerized by reacting a (meth) acryloxy group having a functional group represented by formula (1).
使本發明之聚合物進行聚合時之溫度條件並無特別限制。例如,可為0~150℃。 The temperature conditions at which the polymer of the present invention is polymerized are not particularly limited. For example, it can be 0 ~ 150 ° C.
作為本發明之聚合物之製造方法,例如可列舉以下方法,步驟1:使末端具有含活性氫之基之原料聚合物與聚異氰酸酯發生反應,製造末端具有異氰酸酯基之含異氰酸酯基之聚合物,以及 步驟2:然後,其接著使如上製成之含異氰酸酯基之聚合物,與具有(甲基)丙烯醯氧基和含活性氫之基之含(甲基)丙烯醯氧基之化合物發生反應,製造含(甲基)丙烯醯氧基之聚合物。 As a method for producing the polymer of the present invention, for example, the following method can be enumerated: Step 1: reacting a raw polymer having an active hydrogen-containing group at the terminal and polyisocyanate to produce an isocyanate group-containing polymer having an isocyanate group at the terminal, as well as Step 2: Then, it reacts the isocyanate group-containing polymer prepared above with a (meth) acryloxy group and a (meth) acryloxy group-containing compound having an active hydrogen group, Manufacture of (meth) acrylic fluorenyl-containing polymers.
步驟1係使末端具有含活性氫之基之原料聚合物與聚異氰酸酯發生反應,製造末端具有異氰酸酯基之含異氰酸酯基之聚合物的步驟。含異氰酸酯基聚合物可於至少1個末端或所有末端具有異氰酸酯基。 Step 1 is a step of reacting a base polymer having a terminal group containing an active hydrogen with a polyisocyanate to produce an isocyanate group-containing polymer having an isocyanate group at a terminal. The isocyanate group-containing polymer may have an isocyanate group at at least one terminal or all terminals.
作為步驟1中使用之原料聚合物,例如可列舉作為主鏈之骨架具有由包含選自由丁二烯及異戊二烯所組成之群中至少1種之單體形成之聚合物或其氫化物,並且於末端具有含活性氫之基(例如,羥基)之含活性氫之聚合物。含活性氫之聚合物可於至少1個末端或所有末端具有含活性氫之基。 Examples of the raw material polymer used in step 1 include a polymer having a backbone as a main chain and a polymer thereof including at least one monomer selected from the group consisting of butadiene and isoprene or a hydride thereof. And an active hydrogen-containing polymer having an active hydrogen-containing group (eg, a hydroxyl group) at the terminal. The active hydrogen-containing polymer may have an active hydrogen-containing group at at least one terminal or all terminals.
作為原料聚合物之主鏈之骨架,例如可列舉具有選自由以下述式(Ia)~式(Ic)所表示之重複單元所組成之群中至少1種者,
(式(Ia)~式(Ic)中,虛線與實線之雙重線表示單鍵或雙鍵。) (In the formulae (Ia) to (Ic), the double line of the dashed line and the solid line represents a single bond or a double bond.)
原料聚合物中以式(Ia)所表示之重複單元之含量4與本發明之聚合物中之上述含量1相同。原料聚合物中式(Ib)之含量5與上述含量2相同,原料聚合物中式(Ic)之含量6與上述含量3相同。 The content 4 of the repeating unit represented by the formula (Ia) in the base polymer is the same as the above-mentioned content 1 in the polymer of the present invention. The content 5 of formula (Ib) in the base polymer is the same as the above-mentioned content 2, and the content 6 of formula (Ic) in the base polymer is the same as the above-mentioned content 3.
作為原料聚合物,例如可列舉以下述式(a1)~式(a4)所表示之兩末端含羥基之聚合物,
式(a1)及(a2)中,m分別獨立表示15~90之整數,
式(a3)中,m為0~50之整數。n為0至90之整數,較佳為5~90,m與n之合計可為140以下,較佳為90以 下,m與n不同時為0,式(a4)中,m為10~90之整數。 In formula (a3), m is an integer of 0-50. n is an integer from 0 to 90, preferably 5 to 90, and the total of m and n may be 140 or less, preferably 90 or more In the following, m and n are not 0 at the same time. In formula (a4), m is an integer from 10 to 90.
原料聚合物之數平均分子量較佳為1000~10000,更佳為1500~7000。原料聚合物之數平均分子量係以四氫呋喃為溶劑,藉由聚苯乙烯換算,利用凝膠滲透層析法(GPC)測定而求得之值。 The number average molecular weight of the base polymer is preferably 1,000 to 10,000, and more preferably 1500 to 7000. The number-average molecular weight of the base polymer is a value obtained by measuring with a gel permeation chromatography (GPC) in terms of polystyrene, using tetrahydrofuran as a solvent, and converting it into polystyrene.
原料聚合物可分別單獨或者組合兩種以上使用。 The base polymers can be used individually or in combination of two or more kinds.
步驟1中使用之聚異氰酸酯係分子內具有2個異氰酸酯基者即可,並無特別限制。 The polyisocyanate system used in step 1 may have two isocyanate groups in the molecule, and is not particularly limited.
作為聚異氰酸酯,具體而言,例如可列舉TDI(例如2,4-二異氰酸甲苯酯(2,4-TDI)、2,6-二異氰酸甲苯酯(2,6-TDI))、MDI(例如4,4'-二苯基甲烷二異氰酸酯(4,4'-MDI)、2,4'-二苯基甲烷二異氰酸酯(2,4'-MDI))、1,4-伸苯基二異氰酸酯、苯二亞甲基二異氰酸酯(XDI)、四甲苯二亞甲基二異氰酸酯(TMXDI)、聯甲苯胺二異氰酸酯(TODI)、1,5-萘二異氰酸酯(NDI)、三苯甲基三異氰酸酯等之芳香族二異氰酸酯;六亞甲基二異氰酸酯(HDI)、三甲基六亞甲基二異氰酸酯(TMHDI)、離胺酸二異氰酸酯、降冰片烷二異氰酸酯(NBDI)、反式環己烷-1,4-二異氰酸酯、異佛爾酮二異氰酸酯(IPDI)、雙(異氰酸酯甲基)環己烷(H6XDI)、二環己基甲烷二異氰酸酯(H12MDI)等之脂肪族二異氰酸酯(包含具有脂環式烴基之二異氰酸酯);上述 二異氰酸酯之異氰尿酸酯體、縮二脲體、加成物等。聚異氰酸酯可單獨使用1種,亦可併用2種以上。 Specific examples of the polyisocyanate include TDI (e.g., toluene 2,4-diisocyanate (2,4-TDI), toluene 2,6-diisocyanate (2,6-TDI)) , MDI (such as 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4- Phenyl diisocyanate, xylylene diisocyanate (XDI), tetraxylylene diisocyanate (TMXDI), benzylamine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenyl Aromatic diisocyanates such as methyl triisocyanate; hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), Cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanate methyl) cyclohexane (H 6 XDI), dicyclohexyl methane diisocyanate (H 12 MDI), etc. Aliphatic diisocyanates (including diisocyanates having alicyclic hydrocarbon groups); isocyanurate bodies, biuret bodies, adducts, and the like of the diisocyanates. Polyisocyanate may be used individually by 1 type, and may use 2 or more types together.
原料聚合物與聚異氰酸酯之量比可為含活性氫基與異氰酸酯基之莫耳比(異氰酸酯基/含活性氫基)大於1之數值(例如,1.1~2)。 The amount ratio of the base polymer to the polyisocyanate may be a value (for example, 1.1 to 2) in which the molar ratio (isocyanate group / active hydrogen group-containing) of the active hydrogen group and the isocyanate group is greater than 1.
步驟1中,可藉由將原料聚合物與聚異氰酸酯進行混合,並於氮氣環境下於50~120℃之條件下進行加熱,製造含異氰酸酯基聚合物。 In step 1, an isocyanate group-containing polymer can be produced by mixing a base polymer with a polyisocyanate, and heating the polymer at 50 to 120 ° C. under a nitrogen environment.
再者,步驟1中,由於使具有1個聚異氰酸酯之多個異氰酸酯基與原料聚合物發生反應,所以原料聚合物亦可實現高分子量化。 Furthermore, in step 1, since a plurality of isocyanate groups having one polyisocyanate are reacted with the base polymer, the base polymer can also achieve high molecular weight.
步驟2係使步驟1中所獲得之含異氰酸酯基之聚合物,與具有(甲基)丙烯醯氧基和含活性氫之基之含(甲基)丙烯醯氧基之化合物發生反應,製造含(甲基)丙烯醯氧基之聚合物的步驟。 Step 2 is a step of reacting the isocyanate group-containing polymer obtained in step 1 with a (meth) propenyloxy group and a (meth) propenyloxy group-containing compound containing an active hydrogen group to produce a polymer containing Step of polymer of (meth) acrylic acid.
步驟2中使用之含(甲基)丙烯醯氧基之化合物係具有(甲基)丙烯醯氧基與含活性氫基之化合物。作為含活性氫基,例如可列舉羥基、胺基等。 The (meth) propenyloxy group-containing compound used in step 2 is a compound having a (meth) propenyloxy group and an active hydrogen group-containing compound. Examples of the active hydrogen-containing group include a hydroxyl group and an amino group.
作為含(甲基)丙烯醯氧基之化合物,例如可列舉以下述式(3)所示之化合物,
式(3)中,R31、R32分別單獨表示氫原子或甲基,m3、n3分別單獨表示1~5,X為含活性氫基,式(3)中,m3、n3分別與上述式(1)之m、n相同,含活性氫基X與上述含活性氫基相同。 In formula (3), R 31 and R 32 each independently represent a hydrogen atom or a methyl group, m3 and n3 each independently represent 1 to 5, and X is an active hydrogen-containing group. In formula (3), m3 and n3 are respectively the same as the formula (1) m and n are the same, and the active hydrogen-containing group X is the same as the above-mentioned active hydrogen-containing group.
作為以式(3)所示之化合物,例如可列舉下述式(3-1)所示之化合物,
式(3-1)中,R311、R312、m31、n31分別與上述式(1)之R1、R2、m、n相同。 In the formula (3-1), R 311 , R 312 , m31, and n31 are the same as R 1 , R 2 , m, and n in the formula (1), respectively.
作為以式(3)所表示之化合物,具體而言例如可列舉2-羥基-3-(甲基)丙烯醯氧基丙基(甲基)丙烯酸酯。 Specific examples of the compound represented by the formula (3) include 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate.
步驟2中,作為含(甲基)丙烯醯氧基之化合物,可與以上述式(3)所示之化合物同時使用之其他含(甲基)丙烯醯氧基之化合物。作為其他含(甲基)丙烯醯氧基之化合物,例如可列舉1分子中具有1個(甲基)丙烯醯氧基與含活性氫基之化合物。 In the step 2, as the (meth) acryloxy group-containing compound, other (meth) acryloxy group-containing compounds may be used together with the compound represented by the formula (3). Examples of other (meth) acrylfluorenyl-containing compounds include compounds having one (meth) acrylfluorenyloxy group and an active hydrogen group-containing compound in one molecule.
作為上述其他含(甲基)丙烯醯氧基之化合物,例如可 列舉羥基乙基(甲基)丙烯酸酯、羥基丙基(甲基)丙烯酸酯、羥基丁基(甲基)丙烯酸酯、季戊四醇(甲基)丙烯酸酯、二戊四醇(甲基)丙烯酸酯、三(2-羥基乙基)異氰脲酸酯單(甲基)丙烯酸酯)等具有1個或2個以上羥基之含單(甲基)丙烯醯氧基之化合物。 As the other (meth) acrylic fluorenyloxy-containing compound, for example, Examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol (meth) acrylate, dipentaerythritol (meth) acrylate, Mono (meth) acrylic fluorenyloxy-containing compounds, such as tris (2-hydroxyethyl) isocyanurate mono (meth) acrylate), having one or more hydroxyl groups.
含(甲基)丙烯醯氧基之化合物之製造並無特別限制。例如可列舉以往眾所周知者。此外,作為含(甲基)丙烯醯氧基之化合物,可使用市售商品。以上述式(3-1)所示之化合物可依據例如日本專利特開2007-28995號公報所記載之製造方法進行製造。 The production of the (meth) acrylic fluorenyloxy-containing compound is not particularly limited. For example, a conventionally well-known thing can be mentioned. Moreover, as a (meth) acryl fluorenyl group containing compound, a commercial item can be used. The compound represented by the above formula (3-1) can be produced according to the production method described in, for example, Japanese Patent Laid-Open No. 2007-28995.
相對於步驟2中使用之含(甲基)丙烯醯氧基之化合物之合計,以式(3)所表示之化合物之莫耳比例(以式(3)所示之化合物/步驟2中使用之含(甲基)丙烯醯氧基之化合物之合計)較佳為50莫耳%以上。 The molar ratio of the compound represented by formula (3) to the total of the (meth) acryloxy-group-containing compounds used in step 2 (the compound represented by formula (3) / the compound used in step 2 The total amount of the (meth) acryloxy group-containing compound) is preferably 50 mol% or more.
含(甲基)丙烯醯氧基之化合物可分別單獨或組合2種以上使用。 The (meth) acrylic fluorenyloxy-containing compound may be used alone or in combination of two or more kinds.
相對於上述含異氰酸酯基之聚合物100質量份,含(甲基)丙烯醯氧基之化合物之使用量較佳為1~100質量份,更佳為1~50質量份。 The use amount of the (meth) acryloxy group-containing compound is preferably 1 to 100 parts by mass, and more preferably 1 to 50 parts by mass, with respect to 100 parts by mass of the isocyanate group-containing polymer.
步驟2中,藉由將含異氰酸酯基聚合物和含(甲基)丙烯醯氧基之化合物進行混合,然後於50~120℃之條件下進行加熱,可製成本發明之聚合物。 In step 2, the polymer of the present invention can be prepared by mixing an isocyanate group-containing polymer and a (meth) acrylic fluorenyl group-containing compound, and then heating at 50 to 120 ° C.
如上製成之聚合物亦可為混合物。作為混合物,例如可列舉包含本發明之聚合物2種以上者、含有本發明之聚 合物與本發明之聚合物以外之聚合物(例如後述之聚合物a)者。 The polymers prepared as above can also be mixtures. Examples of the mixture include two or more kinds of the polymer of the present invention and a polymer containing the present invention. And a polymer other than the polymer of the present invention (for example, polymer a) described later.
使用本發明之聚合物,可製成含有其之含(甲基)丙烯醯氧基之聚合物組成物(組成物)。 By using the polymer of the present invention, a polymer composition (composition) containing a (meth) acrylic fluorenyloxy group can be prepared.
作為上述組成物,例如可列舉含有含(甲基)丙烯醯氧基之聚合物(A),與光聚合引發劑之組成物。 Examples of the composition include a composition containing a (meth) acrylic fluorenyl group-containing polymer (A) and a photopolymerization initiator.
上述組成物中,含(甲基)丙烯醯氧基之聚合物(A)(聚合物(A))可將其一部分或全部作為本發明之聚合物。 In the above composition, a part or all of the polymer (A) (polymer (A)) containing a (meth) acrylic alkoxy group may be used as the polymer of the present invention.
作為聚合物(A)之一部分或全部而使用之聚合物與上述本發明之聚合物相同。作為聚合物(A)之一部分或全部而使用之聚合物可分別單獨或組合2種以上使用。 The polymer used as part or all of the polymer (A) is the same as the polymer of the present invention described above. The polymer used as a part or all of the polymer (A) may be used alone or in combination of two or more kinds.
聚合物(A)之一部分為本發明之聚合物時,作為聚合物(A)更進一步可含有之其他含(甲基)丙烯醯氧基之聚合物,例如可列舉所有末端具有1個(甲基)丙烯醯氧基之聚合物a。 When a part of the polymer (A) is the polymer of the present invention, as the polymer (A), other (meth) acryloxy-group-containing polymers may be included. A) acryloxyoxy polymer a.
聚合物a具有主鏈,上述主鏈與(甲基)丙烯醯氧基可直接或透過雜原子或有機基進行鍵結。聚合物a可具有之主鏈之骨架、雜原子、有機基與上述相同。作為聚合物a具有之(甲基)丙烯醯氧基,例如可列舉具有與上述官能基不同之(甲基)丙烯醯氧基之基(其他基)。 The polymer a has a main chain, and the main chain and the (meth) acrylfluorenyl group may be bonded directly or through a hetero atom or an organic group. The backbone, heteroatoms, and organic groups that the polymer a may have are the same as those described above. Examples of the (meth) acrylfluorenyl group which the polymer a has include a group (other group) having a (meth) acrylfluorenyl group different from the functional group described above.
聚合物a之數平均分子量較佳為5,000~100,000,更佳為10,000~70,000。聚合物a之數平均分子量係以四氫呋喃為溶劑,藉由聚苯乙烯換算,利用凝膠滲透層析法(GPC)測定而求得之值。 The number average molecular weight of the polymer a is preferably 5,000 to 100,000, and more preferably 10,000 to 70,000. The number-average molecular weight of the polymer a is a value obtained by measuring by polystyrene conversion using gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
聚合物a之製造並無特別限制。例如,上述聚合物a可為製造本發明之聚合物時生成之副產物。此外,作為聚合物a之製造方法,例如可列舉除了於上述步驟2中將以上述式(3)所示之化合物替換為上述其他含(甲基)丙烯醯氧基之化合物以外,與本發明之聚合物之製造同樣地進行製造,製成聚合物a之方法。 The production of the polymer a is not particularly limited. For example, the above-mentioned polymer a may be a by-product generated when the polymer of the present invention is produced. In addition, as a method for producing the polymer a, for example, in addition to replacing the compound represented by the above formula (3) with the other (meth) acrylic fluorenyloxy-containing compound in the above step 2, the present invention is similar to the present invention The method for producing a polymer is performed in the same manner as in the production of a polymer.
聚合物a可分別單獨或者組合兩種以上使用。 The polymer a can be used alone or in combination of two or more kinds.
聚合物(A)之一部分為本發明之聚合物時,相對於聚合物(A)總量,本發明之聚合物之含量較佳為10~80質量%,更佳為20~65質量%。 When a part of the polymer (A) is the polymer of the present invention, the content of the polymer of the present invention is preferably 10 to 80% by mass, and more preferably 20 to 65% by mass, relative to the total amount of the polymer (A).
此外,上述組成物進一步可列舉含有具有1個(甲基)丙烯醯氧基之單官能(甲基)丙烯酸酯化合物者作為較佳態樣之一。 In addition, as for the said composition, the thing containing the monofunctional (meth) acrylate compound which has one (meth) acryl methoxy group further is mentioned as one of the preferable aspects.
上述單官能(甲基)丙烯酸酯化合物係具有1個(甲基)丙烯醯氧基之化合物即可,並無特別限制。(甲基)丙烯醯氧基可與烴基進行鍵結。烴基並無特別限制。例如可列舉與上述相同者。 The monofunctional (meth) acrylate compound is not particularly limited as long as it is a compound having one (meth) acrylic fluorenyloxy group. The (meth) acrylfluorenyl group may be bonded to a hydrocarbon group. The hydrocarbon group is not particularly limited. For example, the same thing as the above is mentioned.
作為單官能(甲基)丙烯酸酯化合物之具體例, 例如可列舉甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、苄基(甲基)丙烯酸酯、卡必醇(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、環氧丙基(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、十三基(甲基)丙烯酸酯、硬脂醯(甲基)丙烯酸酯、乙氧乙基(甲基)丙烯酸酯、甲氧乙基(甲基)丙烯酸酯、烯丙基(甲基)丙烯酸酯、3-甲氧丁基(甲基)丙烯酸酯、異辛(甲基)丙烯酸酯、苯氧乙基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、異莰基(甲基)丙烯酸酯、異癸基(甲基)丙烯酸酯等。單官能(甲基)丙烯酸酯化合物可單獨使用1種,亦可併用2種以上。 As specific examples of the monofunctional (meth) acrylate compound, Examples include meth (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and carbidine Alcohol (meth) acrylate, 2-ethylhexyl (meth) acrylate, epoxypropyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, Stearyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, allyl (meth) acrylate, 3-methoxybutyl (methyl Base) acrylate, isooctyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isofluorenyl (meth) acrylate, isodecyl (Meth) acrylates and the like. A monofunctional (meth) acrylate compound may be used individually by 1 type, and may use 2 or more types together.
其中,考慮到對上述含(甲基)丙烯醯氧基之聚合物(A)之相溶性良好且耐候性優異之理由,更佳為選自由具有脂環式烴基之化合物、具有鏈狀烴基之化合物、二環戊烯基(甲基)丙烯酸酯、異莰基(甲基)丙烯酸酯以及異癸基(甲基)丙烯酸酯所組成之群中至少1種。 Among these, in consideration of the good compatibility with the (meth) acryloxy group-containing polymer (A) and excellent weather resistance, it is more preferably selected from the group consisting of a compound having an alicyclic hydrocarbon group and a compound having a chain hydrocarbon group. At least one of the group consisting of a compound, a dicyclopentenyl (meth) acrylate, an isofluorenyl (meth) acrylate, and an isodecyl (meth) acrylate.
相對於上述含(甲基)丙烯醯氧基之聚合物(A)100質量份,上述單官能(甲基)丙烯酸酯化合物之含量較佳為10~200質量份,更佳為30~100質量份。 The content of the monofunctional (meth) acrylate compound is preferably 10 to 200 parts by mass, and more preferably 30 to 100 parts by mass relative to 100 parts by mass of the (meth) acryloxy group-containing polymer (A). Serving.
作為上述光聚合引發劑,例如可列舉烷基苯酮系化合物、安息香醚系化合物、二苯基酮系化合物等羰基化合物、硫化合物、偶氮化合物、過氧化物化合物、膦氧化物 系化合物等。 Examples of the photopolymerization initiator include carbonyl compounds such as alkyl phenone compounds, benzoin ether compounds, and diphenyl ketone compounds, sulfur compounds, azo compounds, peroxide compounds, and phosphine oxides. Department of compounds and so on.
更具體而言,例如可列舉苯乙酮、安息香、安息香甲醚、安息香乙醚、安息香異丙基醚、乙偶姻、丁偶姻、甲苯偶姻、苄基、二苯基酮、p-甲氧二苯基酮、二乙氧苯乙酮、α,α-二甲氧-α-苯基苯乙酮、甲苯乙醛酸酯、乙苯乙醛酸酯、4,4'-雙(二甲胺二苯基酮)、2-羥基-2-甲基-1-苯丙烷-1-酮、以下述式(8)所示之1-羥基環己基苯酮等之羰基化合物;一硫化四甲基秋蘭姆、二硫化四甲基秋蘭姆等之硫化合物;偶氮雙異丁腈、偶氮雙-2,4-二甲基戊腈等之偶氮化合物;過氧化苯甲醯、二叔丁基過氧化物等之過氧化物化合物等,這些可單獨使用1種,亦可併用2種以上。 More specifically, for example, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyridine, toluene, benzyl, diphenyl ketone, p-formyl Oxydiphenyl ketone, diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, toluene glyoxylate, glyoxylate, 4,4'-bis (di Methylamine diphenyl ketone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, carbonyl compounds such as 1-hydroxycyclohexyl benzophenone represented by the following formula (8); Sulfur compounds such as methylthiuram and tetramethylthiuram disulfide; azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, etc .; benzamidine peroxide And peroxy compounds such as di-tert-butyl peroxide, etc. These may be used alone or in combination of two or more.
其中,考慮到光穩定性、光碎片化高效率性、與上述含(甲基)丙烯醯氧基之聚合物(A)之相溶性、低揮發性、低臭性之觀點,較佳為1-羥基環己基苯酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、1-〔4-(2-羥基乙氧基)-苯基〕-2-羥基-2-甲基-1-丙烷-1-酮。 Among these, from the viewpoints of light stability, high efficiency of photofragmentation, compatibility with the (meth) acryloxy-group-containing polymer (A), low volatility, and low odor, it is preferably 1 -Hydroxycyclohexylbenzophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2 -Methyl-1-propane-1-one.
作為1-羥基環己基苯酮之市售品,例如可列舉IRGACURE 184(Ciba Specialty Chemicals公司製)。 Examples of commercially available products of 1-hydroxycyclohexylbenzophenone include IRGACURE 184 (manufactured by Ciba Specialty Chemicals).
相對於上述含(甲基)丙烯醯氧基之聚合物 (A)100質量份,上述光聚合引發劑之含量較佳為1~10質量份,更佳為2~8質量份。 Relative to the above (meth) acrylic fluorenyl-containing polymer (A) 100 parts by mass, the content of the photopolymerization initiator is preferably 1 to 10 parts by mass, and more preferably 2 to 8 parts by mass.
考慮到作業性之觀點,上述組成物進一步可含有溶劑。 From the viewpoint of workability, the composition may further contain a solvent.
作為溶劑,具體而言,例如可列舉乙醇、異丙醇、丁醇、甲苯、二甲苯、丙酮、甲基乙基酮、乙酸乙酯、乙酸丁酯、環己酮等。 Specific examples of the solvent include ethanol, isopropanol, butanol, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, and cyclohexanone.
上述組成物可於不損害本發明之目的之範圍內,進一步含有各種添加劑。作為添加劑,例如可列舉本發明之聚合物以外之多官能(甲基)丙烯酸酯、增塑劑、填充劑、抗老化劑、抗氧化劑、抗靜電劑、阻燃劑、增黏劑、調平劑、分散劑、消泡劑、消光劑、光穩定劑(例如,受阻胺類化合物等)、染料、顏料等。 The above-mentioned composition may further contain various additives as long as the object of the present invention is not impaired. Examples of the additives include polyfunctional (meth) acrylates other than the polymer of the present invention, plasticizers, fillers, anti-aging agents, antioxidants, antistatic agents, flame retardants, tackifiers, and leveling agents. Agents, dispersants, defoamers, matting agents, light stabilizers (for example, hindered amine compounds, etc.), dyes, pigments, and the like.
上述組成物製備方法並無特別限制,例如可藉由以下方法等製成:在反應容器內加入上述各種必需成分與可選成分,減壓下使用攪拌混合機等攪拌機充分混勻。 The method for preparing the above composition is not particularly limited. For example, the composition can be prepared by adding the above-mentioned various necessary components and optional components to a reaction container, and mixing them thoroughly using a stirrer such as a stirrer under reduced pressure.
上述組成物可例如藉由光實現硬化性。照射至上述組成物之光並無特別限制。例如可列舉紫外線。 The composition can achieve hardenability by light, for example. The light irradiated to the composition is not particularly limited. Examples include ultraviolet rays.
硬化上述組成物時之溫度條件並無特別限制。例如可為0~150℃。 There are no particular restrictions on the temperature conditions at which the composition is cured. For example, it can be 0 to 150 ° C.
上述組成物例如可作為接著劑使用。作為接著劑,具體而言例如可列舉光學用透明樹脂(OCR:Optical Clear Resin)。OCR例如可黏貼觸摸屏之蓋玻片、透明導電構件、液晶模組等。 The composition can be used as an adhesive, for example. Specific examples of the adhesive include optical clear resin (OCR: Optical Clear Resin). The OCR can be adhered to a cover glass of a touch screen, a transparent conductive member, a liquid crystal module, and the like.
可適用上述組成物之基材(被黏物)並無特別限制。例如可列舉玻璃、塑膠、橡膠、金屬。 The substrate (adhesive) to which the above composition can be applied is not particularly limited. Examples include glass, plastic, rubber, and metal.
以下,使用實施例詳細說明本發明。但本發明並不限定於該等實施例。 Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to these examples.
含(甲基)丙烯醯氧基之聚合物(本發明之聚合物)之製造中,按照第1表所示之量(單位g)使用該表所示之各成分。 In the production of the (meth) acrylic fluorenyl-containing polymer (the polymer of the present invention), each component shown in the table is used in the amount (unit g) shown in the first table.
首先,將各原料聚合物與各聚異氰酸酯進行混合,氮氣環境下於70℃之條件反應5小時,獲得兩末端具有異氰酸酯基之含異氰酸酯之基之聚合物(步驟1)。 First, each raw polymer is mixed with each polyisocyanate, and reacted at 70 ° C. for 5 hours under a nitrogen atmosphere to obtain an isocyanate group-containing polymer having an isocyanate group at both ends (step 1).
然後,於NCO殘量為0.96%以下時,於反應系統內添加各含(甲基)丙烯醯氧基之化合物,於70℃之條件下反應5小時,製成含(甲基)丙烯醯氧基之聚合物(步驟2)。 Then, when the residual NCO content is 0.96% or less, each (meth) acryloxy group-containing compound is added to the reaction system and reacted at 70 ° C for 5 hours to prepare (meth) acryloxy group Based polymer (step 2).
將實施例1中製成之含(甲基)丙烯醯氧基之聚合物設為聚合物(A-1)。此外,其他實施例中製成之聚合物如第1 表所示。 The polymer (A-1) containing the (meth) acrylic fluorenyloxy group prepared in Example 1 was used. In addition, the polymers made in other examples are as As shown in the table.
如上所述製成之含(甲基)丙烯醯氧基之聚合物之構造示於以下述式(5)。 The structure of the (meth) acryloxy-group-containing polymer prepared as described above is shown by the following formula (5).
式(5):〔官能基-胺基甲酸酯鍵51-聚異氰酸酯殘基-胺基甲酸酯鍵52〕2-原料聚合物殘基 Formula (5): [functional group-urethane bond 51 -polyisocyanate residue-urethane bond 52 ] 2 -base polymer residue
式(5)中,原料聚合物殘基相當於含(甲基)丙烯醯氧基之聚合物之主鏈。如上述所製成之聚合物具有來自原料聚合物之主鏈。如上述所製成之聚合物之主鏈亦可為具有原料聚合物之二聚體以上者。此時,如上述所製成之聚合物之主鏈除了胺基甲酸酯鍵51及胺基甲酸酯鍵52以外,亦可包含來自製造時所使用之聚異氰酸酯之胺基甲酸酯鍵。 In formula (5), the base polymer residue corresponds to the main chain of the (meth) acrylic fluorenyl group-containing polymer. The polymer prepared as described above has a main chain derived from the base polymer. The main chain of the polymer produced as described above may also be a dimer or more having a raw polymer. At this time, in addition to the urethane bond 51 and the urethane bond 52 , the main chain of the polymer prepared as described above may include a urethane bond derived from the polyisocyanate used in the production .
此外,式(5)中,「胺基甲酸酯鍵51-聚異氰酸酯殘基-胺基甲酸酯鍵52」之部分相當於有機基。 Further, in the formula (5), the portion of "urethane bond 51 -polyisocyanate residue-urethane bond 52 " corresponds to an organic group.
聚合物(A-1)具有之官能基2個皆為下述式(1-1)所表示之基。 The two functional groups possessed by the polymer (A-1) are both groups represented by the following formula (1-1).
聚合物(A-1)之含量1為10莫耳%,含量2為90莫耳%。 The content 1 of the polymer (A-1) was 10 mol%, and the content 2 was 90 mol%.
再者,聚異氰酸酯殘基為異佛爾酮二異氰酸酯殘基。 The polyisocyanate residue is an isophorone diisocyanate residue.
聚合物(A-1)之數平均分子量為23,000。 The number average molecular weight of the polymer (A-1) was 23,000.
聚合物(A-2)之官能基兩個皆為以上述式(1-1)所表示 之基。 Both functional groups of the polymer (A-2) are represented by the above formula (1-1) The base.
聚合物(A-2)之含量1為15莫耳%,含量2為85莫耳%。 The content 1 of the polymer (A-2) was 15 mol%, and the content 2 was 85 mol%.
聚合物(A-2)之數平均分子量為23,000。 The number average molecular weight of the polymer (A-2) was 23,000.
聚合物(A-3)係含聚合物(A-3-1)、聚合物(A-3-2)以及聚合物(A-3-3)之混合物。 The polymer (A-3) is a mixture containing the polymer (A-3-1), the polymer (A-3-2), and the polymer (A-3-3).
聚合物(A-3-1)~(A-3-3)除官能基以外皆相同。 The polymers (A-3-1) to (A-3-3) are all the same except for the functional group.
聚合物(A-3)之含量1為35莫耳%,含量2為65莫耳%。 The content 1 of the polymer (A-3) was 35 mol%, and the content 2 was 65 mol%.
聚合物(A-3-1)具有之官能基2個都為以上述式(1-1)所表示之基。 The polymer (A-3-1) has two functional groups each represented by the formula (1-1).
聚合物(A-3-2)具有之1個官能基為以上述式(1-1)所示之基,剩餘1個為以下述式(2-1)所表示之基。 One functional group of the polymer (A-3-2) is a group represented by the above formula (1-1), and the remaining one is a group represented by the following formula (2-1).
聚合物(A-3-3)具有之官能基2個都為以上述式(2-1)所示之基。 Both of the functional groups possessed by the polymer (A-3-3) are groups represented by the formula (2-1).
聚合物(A-4)係含聚合物(A-4-1)、聚合物(A-4-2)以及聚合物(A-4-3)之混合物。 The polymer (A-4) is a mixture containing the polymer (A-4-1), the polymer (A-4-2), and the polymer (A-4-3).
聚合物(A-4-1)~(A-4-3)除官能基以外皆相同。 The polymers (A-4-1) to (A-4-3) are all the same except for the functional group.
聚合物(A-4)之含量1為35莫耳%,含量2為65莫耳%。 The content 1 of the polymer (A-4) was 35 mol%, and the content 2 was 65 mol%.
聚合物(A-4-1)具有之官能基2個皆為以下述式(1-2)所表示之基。 Both of the functional groups possessed by the polymer (A-4-1) are groups represented by the following formula (1-2).
聚合物(A-4-2)具有之1個官能基為以上述式(1-2)所示之基,剩餘1個為以上述式(2-1)所表示之基。 One functional group of the polymer (A-4-2) is a group represented by the above formula (1-2), and the remaining one is a group represented by the above formula (2-1).
聚合物(A-4-3)具有之官能基2個皆為以上述式(2-1)所表示之基。 The two functional groups of the polymer (A-4-3) are both groups represented by the above formula (2-1).
聚合物(A-5) Polymer (A-5)
聚合物(A-5)之官能基2個都為以上述式(1-1)所示之基。 Both of the functional groups of the polymer (A-5) are groups represented by the formula (1-1).
聚合物(A-5)之含量1為35莫耳%,含量2為65莫耳%。再者,聚異氰酸酯殘基為六亞甲基二異氰酸酯殘基。 The content 1 of the polymer (A-5) was 35 mol%, and the content 2 was 65 mol%. The polyisocyanate residue is a hexamethylene diisocyanate residue.
聚合物(A-6)之官能基兩個都為以上述式(1-1)所示之 基。 Both functional groups of the polymer (A-6) are those represented by the above formula (1-1) base.
聚合物(A-6)之含量1為10莫耳%,含量2為90莫耳%。再者,聚異氰酸酯殘基為異佛爾酮二異氰酸酯殘基。 The content 1 of the polymer (A-6) was 10 mol%, and the content 2 was 90 mol%. The polyisocyanate residue is an isophorone diisocyanate residue.
聚合物(A-7)之官能基2個都為以上述式(1-1)所示之基。 Both of the functional groups of the polymer (A-7) are groups represented by the formula (1-1).
聚合物(A-7)之含量3為100莫耳%。再者,聚異氰酸酯殘基為異佛爾酮二異氰酸酯殘基。 The content (3) of the polymer (A-7) was 100 mol%. The polyisocyanate residue is an isophorone diisocyanate residue.
比較聚合物(E-1)之官能基2個都為以上述式(2-1)所示之基。 Both functional groups of the comparative polymer (E-1) were groups represented by the formula (2-1).
比較聚合物(E-1)之含量1為10莫耳%,含量2為90莫耳%。再者,聚異氰酸酯殘基為異佛爾酮二異氰酸酯殘基。 The content of the comparative polymer (E-1) was 10 mol%, and the content 2 was 90 mol%. The polyisocyanate residue is an isophorone diisocyanate residue.
比較聚合物(E-2)之官能基2個都為以下述式(2-2)所示之基。 Both functional groups of the comparative polymer (E-2) were groups represented by the following formula (2-2).
比較聚合物(E-2)之含量1為10莫耳%,含量2為90莫耳%。再者,聚異氰酸酯殘基為異佛爾酮二異氰酸酯殘基。 The content 1 of the comparative polymer (E-2) was 10 mol%, and the content 2 was 90 mol%. The polyisocyanate residue is an isophorone diisocyanate residue.
第1表所示各成分具體如下。 Each component shown in Table 1 is as follows.
再者,相對於構成各原料聚合物之主鏈之以式(Ia)~式(Ic)所表示之重複單元之合計,以式(Ia)所示之重複單元之含量表示含量4。式(Ib)所示之重複單元之含量表示含量5,式(Ic)所示之重複單元之含量表示含量6。 In addition, content 4 is represented by the content of the repeating unit represented by Formula (Ia) with respect to the total of the repeating unit represented by Formula (Ia)-Formula (Ic) which comprises the main chain of each base polymer. The content of the repeating unit represented by the formula (Ib) represents a content of 5, and the content of the repeating unit represented by the formula (Ic) represents a content of 6.
按照特開2007-28995號公報(實施例2)所記載之製造方法,藉由使甘油與丙烯酸甲酯於極性有機溶劑中脂肪酶之存在下產生酯交換反應,製成含(甲基)丙烯醯氧基之化合物2。 According to the production method described in Japanese Patent Application Laid-Open No. 2007-28995 (Example 2), glycerol and methyl acrylate are subjected to a transesterification reaction in the presence of a lipase in a polar organic solvent to produce (meth) propylene Zingoxy compound 2.
將下述第3表或第5表所示之各成分,按照該表所示之組成(質量份),用攪拌機進行混合,獲得各組成物。 Each component shown in the following Table 3 or Table 5 was mixed with a mixer according to the composition (parts by mass) shown in the table to obtain each composition.
按照以下所示之硬化條件,將如上述所獲得之各組成物硬化後,獲得硬化物。 Each composition obtained as described above is cured under the curing conditions shown below to obtain a cured product.
於玻璃板上0.3mm之厚度之方式塗佈上述各組成物,製成樣品。 Each composition was coated on a glass plate to a thickness of 0.3 mm to prepare a sample.
使用光照射裝置(GS UVSYSTEM TYPE S250-01、GS Yuasa lighting公司製),以光量120mW/cm、累計光量1000mJ/cm2,於氮氣流通下、於23℃之條件,對如上述所製成之樣品照射紫外線(光源:金屬鹵化物燈、波長250~380nm),使組成物硬化。 A light irradiation device (GS UVSYSTEM TYPE S250-01, manufactured by GS Yuasa lighting) was used, under conditions of 23 ° C under a nitrogen flow, at a light amount of 120 mW / cm and a cumulative light amount of 1000 mJ / cm 2 . The sample was irradiated with ultraviolet light (light source: metal halide lamp, wavelength 250-380 nm) to harden the composition.
利用FT-IR(傅里葉轉換紅外光譜)對上述硬化前後之樣品分別實施測定,並按照以下方法評估其聚合度。利用KBr壓片法將硬化前後之樣品分別壓片,並將其作為上述測定之試料使用。 FT-IR (Fourier transform infrared spectroscopy) was used to measure the samples before and after the hardening, and the degree of polymerization was evaluated according to the following method. The KBr tableting method was used to tablet the samples before and after hardening, and this was used as the sample for the above measurement.
FT-IR之810cm-1之吸光度來自(甲基)丙烯醯基之乙 烯基(雙鍵部位)。 The absorbance of 810 cm -1 of FT-IR is derived from the vinyl (double bond site) of (meth) acrylfluorenyl.
即,將硬化前(組成物)之初期狀態(810cm-1之峰強度為最強)時設為聚合度為0%,將硬化(聚合)完全進行後之狀態(810cm-1之峰強度為0)時設為上述聚合度為100%,對於上述硬化前後之樣品,將所測定之上述峰強度之吸光度代入下述式中,計算出聚合度。結果如第3表、第5表所示。 That is, the initial state (the peak intensity at 810 cm -1 is the strongest) before curing (the composition) is set to 0%, and the state after the curing (polymerization) is completely completed (the peak intensity at 810 cm -1 is 0). In the case of), the degree of polymerization is 100%. For the samples before and after the hardening, the measured absorbance of the peak intensity is substituted into the following formula to calculate the degree of polymerization. The results are shown in Tables 3 and 5.
聚合度(%)=100-(硬化後之樣品之上述峰強度之吸光度/硬化前之樣品之上述峰強度之吸光度) Degree of polymerization (%) = 100- (Absorbance of the above peak intensity of the sample after hardening / Absorbance of the above peak intensity of the sample before hardening)
可認為聚合度越大則硬化速度越快。 It is considered that the higher the degree of polymerization, the faster the hardening speed.
第3表所示各成分具體如下。 Each component shown in Table 3 is as follows.
由第3表所示之結果可以看出,不含規定之含(甲基)丙烯醯氧基之聚合物之比較例3、4之硬化速度慢。 From the results shown in Table 3, it can be seen that Comparative Examples 3 and 4 which do not contain a prescribed (meth) acrylic fluorenyl-containing polymer have a slow curing rate.
相對於此,實施例8~16之硬化速度快。 In contrast, Examples 8 to 16 have fast curing speeds.
此外,將實施例8、9、12、13與實施例14進行比較時,還可以看出,主鏈為聚丁二烯或其氫化物之實施例8、9、12、13之硬化速度亦快於主鏈為聚異戊二烯之實施例14。 In addition, when comparing Examples 8, 9, 12, 13 and Example 14, it can also be seen that the hardening speeds of Examples 8, 9, 12, 13 whose main chain is polybutadiene or its hydride are also Faster than Example 14 where the main chain was polyisoprene.
將實施例10~12進行比較時,還可以看出,相對於製造含(甲基)丙烯醯氧基之聚合物時使用之含(甲基)丙烯醯氧基之化合物之合計,特定之含(甲基)丙烯醯氧基之化合物之莫耳比率越大,即本發明之聚合物具有之規定官能基之量越多,則硬化速度越快。 When comparing Examples 10 to 12, it can also be seen that the specific content of the (meth) acryloxy group-containing compound used in the production of the (meth) acryloxy group-containing polymer is specific. The larger the molar ratio of the (meth) acrylic fluorenyl compound, that is, the greater the amount of the prescribed functional group of the polymer of the present invention, the faster the hardening speed.
第5表所示各成分具體如下。 Each component shown in Table 5 is as follows.
由第5表所示之結果可以看出,不含規定之含(甲基)丙烯醯氧基之聚合物之比較例5、6之硬化速度慢。 From the results shown in Table 5, it can be seen that Comparative Examples 5 and 6 which do not contain the prescribed (meth) acrylic fluorenyl-containing polymer have a slow curing rate.
相對於此,實施例17~28之硬化速度快。 In contrast, Examples 17 to 28 have fast curing speeds.
此外,將實施例22、23、26、27與實施例28進行比較時,亦可以看出,主鏈為聚丁二烯或其氫化物之實施例22、23、26、27較主鏈為聚異戊二烯之實施例28硬化速度較快。 In addition, when comparing Examples 22, 23, 26, and 27 with Example 28, it can also be seen that Examples 22, 23, 26, and 27 whose main chain is polybutadiene or its hydride are The polyisoprene Example 28 hardened faster.
此外,將實施例22與實施例27進行比較時,主鏈為聚丁二烯之氫化物之實施例22較主鏈為聚丁二烯之實施例27硬化速度較快。 In addition, when Example 22 is compared with Example 27, Example 22 whose main chain is a polybutadiene hydride hardens faster than Example 27 whose main chain is polybutadiene.
將實施例24~26進行比較時,亦可以看出,相對於製造含(甲基)丙烯醯氧基之聚合物時使用之含(甲基)丙烯醯氧基之化合物之合計,特定之含(甲基)丙烯醯氧基之化合 物之莫耳比率越大,即本發明之聚合物具有之規定官能基之量越多,則硬化速度越快。 When comparing Examples 24 to 26, it can also be seen that the specific content of the (meth) acryloxy group-containing compound used in the production of the (meth) acryloxy group-containing polymer Compound of (meth) acrylic acid The larger the molar ratio of the material, that is, the greater the amount of the prescribed functional group that the polymer of the present invention has, the faster the hardening speed.
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