LOWLY LACTONE-MODIFIED REACTIVE MONOMER COMPOSITION, ACRYLIC POLYOL RESINS PRODUCED WITH THE SAME, CURABLE RESIN COMPOSITIONS AND COATING COMPOSITIONS
申请人:DAICEL CHEMICAL INDUSTRIES, Ltd.
公开号:EP1227113A1
公开(公告)日:2002-07-31
The present invention Nos. I and II relate to a hydroxyalkyl(meth)acrylate composition (a) modified by a small amount of lactones in which a proportion of monomers having two or more continuous chains (n≧2) of lactone is less than 50% (area % by GPC) which is obtained by a ring-opening polymerization of a lactone with a hydroxyalkyl(meth)acrylate, a method for the preparation thereof, and an acrylic polyol resin using thereof,
(in the formula, R, R1, R2, and R3 are independently a hydrogen or a methyl group, "j" is an integer of 2-6, xn pieces of R4 and R5 are independently a hydrogen atom or an alkyl group having a carbon number of 1-12, "x" is 4-7, "n" is 0 or an integer of not less than 1, and an average value of "n" in the composition is not less than 0.3 to less than 1.0).
By allowing to react the composition with other ethylenic unsaturated monomer and to formulate with a commonly-used crosslinking agent and other commonly-used components, there can be obtained a well-balanced high quality finishing agent for industries, an ultraviolet ray- or electron beam-curable coating agent, a composition which can be modified for a reactive improver, etc., and an acrylic polyol resin using thereof.
The present invention No. III relates to a curable resin composition containing 0.5-80 parts by weight of an acrylic polyol resin (A) obtained using a hydroxyalkyl(meth)acrylate composition (a) modified by a small amount of lactones and 0.5-50 parts by weight of a melamine resin (B) [total of the (A) and (B) does not exceed 100 parts by weight] as essential components.
By the composition, even in a melamine-based curing system which is low in price, there can be obtained a curable-type coating composition in which an acid resistance is improved and highly well-balanced between an acid resistance and abrasion resistance, and which is also excellent in flexural resistance and adhesion in recoating.
The present invention No. IV relates to a curable resin composition containing 0.5-80 parts by weight of an acrylic polyol resin (A) containing a hydroxyalkyl(meth)acrylate composition (a) modified by a small amount of lactones as a polymerizing component and 0.5-50 parts by weight of a melamine resin (B) [total of the (A) and (B) does not exceed 100 parts by weight] as essential components.
By the composition, even in a melamine-based curing system which is low in price, there can be obtained a curable-type coating composition in which an acid resistance is improved and highly well-balanced between an acid resistance and abrasion resistance.
The present invention No. V relates to a curable resin composition containing 0.5-80 parts by weight of an acrylic polyol resin (A) obtained using a hydroxyalkyl (meth)acrylate composition (a) modifiedbya small amount of lactones and 0.5-50 parts by weight of a polyisocyanate compound (B) [total of the (A) and (B) does not exceed 100 parts by weight] as essential components.
By the composition, even in an isocyanate-based curing system, there can be obtained a curable-type coating composition in which a pot life is long and workability is improved, and which is highly well-balanced between an acid resistance and abrasion resistance, and which can provide a coating layer which is excellent also in flexural resistance and adhesion in recoating.
The present invention No. VI relates to a curable resin composition containing 0.5-80 parts by weight of an acrylic polyol resin (A) obtained using a hydroxyalkyl(meth)acrylate composition (a) modified by a small amount of lactones and 0.5-50 parts by weight of a polyisocyanate compound (B) [total of the (A) and (B) does not exceed 100 parts by weight] as essential components.
By the composition, even in an isocyanate-based curing system, there can be obtained a curable-type coating composition in which a pot life is long and workability is improved, and which is highly well-balanced between an acid resistance and abrasion resistance, and which can provide a coating layer which is excellent also in flexural resistance and adhesion in recoating.
The present invention No. VII relates to a thermosetting resin composition containing 2-50 parts of an acrylic polyol resin obtained using a hydroxyalkyl(meth)acrylate composition (a) modified by a small amount of lactones and 30-80 parts of an acrylic copolymer having an alkoxysilyl group.
By the composition, there can be obtained a thermosetting resin composition in which crosslinking density is elevated and hardness and abrasion resistance are improved as well as solving a problem of acid resistance and odor.
The present invention No. VIII relates to a carboxylic group-contained acrylate composition (a') modified by a small amount of lactones represented by a formula described below by allowing to react a hydroxyalkyl(meth)acrylate composition (a) modified by a small amount of lactones with a carboxylic anhydride,
(in the formula, R, R1, R2, and R3 are independently a hydrogen or a methyl group, "j" is an integer of 2-6, xn pieces of R4 and R5 are independently a hydrogen atom or an alkyl group having a carbon number of 1-12, "x" is 4-7, "n" is 0 or an integer of not less than 1, an average value of "n" in the composition is not less than 0.3 to less than 1.0, R6 is a residual group of a carboxylic acid, and "m" is an integer of 1-3), and relates to a method for the preparation thereof.
By the method, there can be readily, efficiently, and economically obtained the carboxylic group-contained acrylate monomer composition modified by a small amount of lactones.
The present invention No. IX relates to a curable resin composition containing 10-70 parts of an acrylic polycarboxylic resin essentially containing the carboxylic group-contained hydroxy(meth)acrylate monomer composition (a') modified by a small amount of lactones as a polymerizing component and. 0.5-80 parts of a polyepoxide.
By the composition, there can be obtained a curable-type resin composition which can form a coating layer which is excellent in acid resistance, abrasion resistance, yellowing resistance, and outer appearance, and which is curable at a low temperature.
The present invention No. X relates to a polyester unsaturated monomer (a'') modified by a small amount of lactones in which less than 1 mol of ε-caprolactone is allowed to react with 1 mol of a radically polymerizable unsaturated monomers containing carboxylic group under the presence of an acidic catalyst, and relates to a method for the preparation thereof. By the method, there can be readily and industrially prepared the monomer in a short step.
本发明I和II涉及通过环氧化学反应以少量的内酯改性羟烷基(甲基)丙烯酸酯的改性羟烷基(甲基)丙烯酸酯组合物(a),其中具有两个或更多连续链(n≧2)的内酯单体的比例小于50%(GPC测定的面积%)。该组合物是通过将内酯与羟烷基(甲基)丙烯酸酯进行开环聚合反应而获得的。本发明还涉及该组合物的制备方法,以及使用该组合物的丙烯酸聚醇树脂。
(在公式中,R、R1、R2、R3分别代表氢或甲基;“j”为2-6的整数;“n”个R4和R5分别代表氢原子或碳数为1-12的烷基;“x”为4-7;“n”为0或至少1的整数;且“n”在组合物中的平均值不小于0.3且小于1.0)。
通过将该组合物与其他乙烯基不饱和单体反应,并与常用交联剂和其他常用组分配制,可以得到均衡的高品质工业用涂覆剂、紫外线或电子束固化的涂覆剂、可被改性为反应促进剂的组合物等,以及使用前述组合物的丙烯酸聚醇树脂。
本发明III涉及一种可固化树脂组合物,其中包含0.5-80重量份由少量内酯改性的羟烷基(甲基)丙烯酸酯组合物(a)制得的丙烯酸聚醇树脂(A),以及0.5-50重量份的密胺树脂(B)(A和B的总重量不超过100份)。
即使在价格低廉的密胺固化体系中,该组合物也能提供一种可固化的涂覆组合物,其中酸耐受性得以改善,且酸耐受性与耐磨性高度均衡,同时具有优异的弯曲耐受性和涂复后的附着力。
本发明IV涉及一种可固化树脂组合物,其中包含0.5-80重量份含有少量内酯改性的羟烷基(甲基)丙烯酸酯组合物(a)作为聚合组分的丙烯酸聚醇树脂(A),以及0.5-50重量份的密胺树脂(B)(A和B的总重量不超过100份)。
即使在价格低廉的密胺固化体系中,该组合物也能提供一种可固化的涂覆组合物,其中酸耐受性得以改善,且酸耐受性与耐磨性高度均衡。
本发明V涉及一种可固化树脂组合物,其中包含0.5-80重量份由少量内酯改性的羟烷基(甲基)丙烯酸酯组合物(a)制得的丙烯酸聚醇树脂(A),以及0.5-50重量份的异氰酸酯类化合物(B)(A和B的总重量不超过100份)。
即使在异氰酸酯固化体系中,该组合物也能提供一种可固化的涂覆组合物,其中混合寿命长、操作性得到改善,并在酸耐受性与耐磨性之间高度均衡,且能够提供优异的弯曲耐受性和涂复后附着力的涂覆层。
本发明VI涉及一种可固化树脂组合物,其中包含0.5-80重量份由少量内酯改性的羟烷基(甲基)丙烯酸酯组合物(a)制得的丙烯酸聚醇树脂(A),以及0.5-50重量份的异氰酸酯类化合物(B)(A和B的总重量不超过100份)。
即使在异氰酸酯固化体系中,该组合物也能提供一种可固化的涂覆组合物,其中混合寿命长、操作性得到改善,并在酸耐受性与耐磨性之间高度均衡,且能够提供优异的弯曲耐受性和涂复后附着力的涂覆层。
本发明VII涉及一种热固性树脂组合物,其中包含2-50份由少量内酯改性的羟烷基(甲基)丙烯酸酯组合物(a)制得的丙烯酸聚醇树脂,以及30-80份含有烷氧硅基团的丙烯酸共聚物。
通过该组合物,可以得到一种热固性树脂组合物,其中交联密度提高,硬度和耐磨性得以改善,同时解决了酸耐受性和气味问题。
本发明VIII涉及通过使少量内酯改性的羟烷基(甲基)丙烯酸酯组合物(a)与羧酸酐反应,由下述公式表示的少量内酯改性的含羧酸基团的丙烯酸酯组合物(a')。
(在公式中,R、R1、R2、R3分别代表氢或甲基;“j”为2-6的整数;“n”个R4和R5分别代表氢原子或碳数为1-12的烷基;“x”为4-7;“n”为0或至少1的整数;且“n”在组合物中的平均值不小于0.3且小于1.0;R6为羧酸的剩余基团,“m”为1-3的整数)。
本发明还涉及该组合物的制备方法。
通过该方法,可以方便、高效且经济地制得少量内酯改性的含羧酸基团的丙烯酸酯单体组合物。
本发明IX涉及一种可固化树脂组合物,其中包含10-70份以少量内酯改性的含羧酸基团的羟烷基(甲基)丙烯酸酯单体组合物(a')作为聚合组分的丙烯酸多羧基树脂,以及0.5-80份的环氧树脂。
通过该组合物,可以得到一种可固化的树脂组合物,其能够形成具有优异酸耐受性、耐磨性、抗黄变性和外观的涂覆层,并能够在低温下固化。
本发明X涉及一种通过在酸性催化剂存在下,使少于1摩尔的ε-己内酯与1摩尔的含有羧酸基团的自由基聚合用不饱和单体反应,由少量内酯改性的聚酯不饱和单体(a')。
本发明还涉及该单体的制备方法。
通过该方法,可以在工业规模上快速制得该单体,步骤简洁。