TWI778076B

TWI778076B - Copolymer, resin composition, treatment agent and processed product

Info

Publication number: TWI778076B
Application number: TW107119958A
Authority: TW
Inventors: 川原勇汰; 深瀨一成; 中川康宏
Original assignee: 日商昭和電工股份有限公司
Priority date: 2017-06-27
Filing date: 2018-06-11
Publication date: 2022-09-21
Also published as: CN110869401A; JP7199351B2; JPWO2019003814A1; KR20200020806A; CN110869401B; TW201906881A; WO2019003814A1; KR102355314B1

Abstract

A copolymer which includes a structural component originated from a phosphorous-including unsaturated monomer (A) and a structural component originated from a polymerizable unsaturated monomer (B), wherein the structural component originated from a polymerizable unsaturated monomer (B) includes a structural component originated from an unsaturated carboxylic acid monomer (b-1) having a main chain, wherein the total of the number of carbon atom and the number of oxygen atom is 4 to 10, and wherein the amount of a structural component originated from a (meth)acrylic acid alkyl ester monomer (b-2), which has an alkyl group with a carbon number of 1 to 4, is 0.00 to 1.00 % by mass with respect to the total of the amount of the structural component originated from the phosphorous-including unsaturated monomer (A) and the amount of the structural component originated from the polymerizable unsaturated monomer (B).

Description

共聚物、樹脂組成物、處理劑及加工品Copolymers, resin compositions, treatment agents, and processed products

本發明關於共聚物、樹脂組成物、處理劑及加工品。　　本申請案係基於2017年6月27日在日本申請的特願2017-125089號，主張優先權，在此援用其內容。The present invention relates to a copolymer, a resin composition, a treatment agent, and a processed product. This application claims priority based on Japanese Patent Application No. 2017-125089 filed in Japan on June 27, 2017, the content of which is incorporated herein by reference.

在基材上附著有紙處理劑、纖維處理劑、黏接著劑等處理劑之加工品(以下，亦稱為「加工品等」)係廣泛使用於建築材料、家電、電子材料、汽車等的車輛內裝材料等用途。於加工品等所使用的處理劑之材料中，作為物性提高劑、黏結劑或分散劑，廣泛使用合成樹脂。Processed products (hereinafter, also referred to as "processed products, etc.") to which treatment agents such as paper treatment agents, fiber treatment agents, and adhesives are adhered to the substrate are widely used in construction materials, home appliances, electronic materials, automobiles, and the like. Vehicle interior materials, etc. Synthetic resins are widely used as materials for processing agents used in processed products, etc., as physical property improvers, binders, or dispersants.

近年來，從安全性之觀點來看，要求加工品等的難燃化。作為將加工品等予以難燃化之方法，可舉出作為於加工品等所使用的處理劑，使用包含難燃劑者之方法。　　作為難燃劑，已知紅磷、三氧化銻、氫氧化鋁、氫氧化鎂等之無機系難燃劑；五溴聯苯、八溴聯苯、十溴聯苯等之鹵素系難燃劑；磷酸鹽、磷酸胍、磷酸三苯酯、胺磺酸等之非鹵素難燃劑等。In recent years, from the viewpoint of safety, flame retardancy of processed products and the like has been demanded. As a method of making a processed product etc. flame-retardant, the method of using what contains a flame-retardant agent as a processing agent used for a processed product etc. is mentioned. As flame retardants, inorganic flame retardants such as red phosphorus, antimony trioxide, aluminum hydroxide, magnesium hydroxide, etc.; halogen flame retardants such as pentabromobiphenyl, octabromobiphenyl, and decabromobiphenyl are known. ; Non-halogen flame retardants such as phosphate, guanidine phosphate, triphenyl phosphate, amine sulfonic acid, etc.

鹵素系難燃劑具有優異的難燃化性能。因此，使用鹵素系難燃劑作為難燃劑時，多可以使難燃劑的使用量成為比較少量。因此，於使用包含鹵素系難燃劑的處理劑所製造的加工品等中，難燃劑賦予加工品等物性之影響較少。Halogen-based flame retardants have excellent flame retardant properties. Therefore, when a halogen-based flame retardant is used as the flame retardant, the amount of the flame retardant used can be made relatively small in many cases. Therefore, in the processed product etc. manufactured using the processing agent containing a halogen-type flame retardant, the flame retardant has little influence on physical properties, such as a processed product.

然而，鹵素系難燃劑含有氯或溴、氟等的鹵素元素。因此，若焚化包含鹵素系難燃劑的加工品等，則有產生戴奧辛或鹵化氫等有害物質之虞。因此，鹵素系難燃劑係在以EU諸國為首的世界各國，進行管制或使用的重新評估。　　又，廣泛已知鹵素系難燃劑係與銻化合物併用藉此展現更高的難燃性。因此，鹵素系難燃劑多與銻化合物併用而使用。然而，近年來，關於銻化合物，亦開始進行管制或使用的重新評估，有避免其使用的傾向。However, the halogen-based flame retardant contains halogen elements such as chlorine, bromine, and fluorine. Therefore, when a processed product or the like containing a halogen-based flame retardant is incinerated, there is a possibility that harmful substances such as dioxin and hydrogen halide are generated. Therefore, halogen-based flame retardants are being regulated or re-evaluated in countries around the world including EU countries. In addition, it is widely known that halogen-based flame retardants are used in combination with antimony compounds to exhibit higher flame retardancy. Therefore, halogen-based flame retardants are often used in combination with antimony compounds. However, in recent years, antimony compounds have also begun to be regulated or re-evaluated, and there is a tendency to avoid their use.

與鹵素系難燃劑比較，非鹵素系有機難燃劑係安全性優異。作為非鹵素系有機難燃劑，大多檢討由磷系化合物所構成之磷系難燃劑。　　然而，一般而言，磷系難燃劑之難燃化性能係比鹵素系難燃劑更低。因此，使用磷系難燃劑作為難燃劑時，為了得到充分的難燃性，多必須大量地使用難燃劑。因此，於使用包含磷系難燃劑的處理劑之加工品等中，由於需要多地摻合難燃劑，有加工品等的抗滲出性及抗黏連性不足之情況。Compared with halogen-based flame retardants, non-halogen-based organic flame retardants are superior in safety. As the non-halogen-based organic flame retardant, a phosphorus-based flame retardant composed of a phosphorus-based compound has been reviewed in many cases. However, in general, the flame retardant performance of phosphorus-based flame retardants is lower than that of halogen-based flame retardants. Therefore, when a phosphorus-based flame retardant is used as the flame retardant, it is often necessary to use a large amount of the flame retardant in order to obtain sufficient flame retardant properties. Therefore, in processed products etc. using the treating agent containing a phosphorus-based flame retardant, since a large amount of flame retardant needs to be blended, the processed products and the like may have insufficient bleed resistance and blocking resistance.

專利文獻1中提案有由包含特定量的磷之單體與丙烯酸系不飽和單體及乙酸乙烯酯單體之三元共聚物所構成的難燃性共聚合樹脂。　　專利文獻2中提案將有具有磷酸基或亞磷基的不飽和單體、(甲基)丙烯酸烷酯單體與丙烯酸系不飽和單體予以共聚合而得之樹脂組成物、使用此而加工的紙及纖維加工品。 [先前技術文獻] [專利文獻]Patent Document 1 proposes a flame-retardant copolymer resin composed of a terpolymer of a monomer containing a specific amount of phosphorus, an acrylic unsaturated monomer, and a vinyl acetate monomer. Patent Document 2 proposes a resin composition obtained by copolymerizing an unsaturated monomer having a phosphoric acid group or a phosphorous group, an alkyl (meth)acrylate monomer, and an acrylic unsaturated monomer, and processing using this paper and fiber products. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開平7-18028號公報　　[專利文獻2]日本特開2010-235830號公報[Patent Document 1] Japanese Patent Laid-Open No. 7-18028 [Patent Document 2] Japanese Patent Laid-Open No. 2010-235830

[發明所欲解決的課題][Problems to be solved by the invention]

然而，以往之包含難燃性樹脂的加工品，無法滿足難燃性、抗滲出性及抗黏連性之全部。However, conventional processed products containing flame retardant resins cannot satisfy all of flame retardancy, bleed resistance and blocking resistance.

本發明係鑒於上述情事而完成者，其課題在於提供難燃性優異，抗滲出性及抗黏連性良好之樹脂。　　又，本發明之課題在於提供能得到具有良好的難燃性、抗滲出性及抗黏連性之塗膜的樹脂組成物及處理劑。　　另外，本發明之課題在於提供具有優異的難燃性、抗滲出性及抗黏連性之加工品。 [解決課題的手段]The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a resin having excellent flame retardancy and excellent bleed resistance and blocking resistance. Furthermore, an object of the present invention is to provide a resin composition and a treatment agent that can obtain a coating film having good flame retardancy, bleed resistance and blocking resistance. In addition, an object of the present invention is to provide a processed product having excellent flame retardancy, bleed resistance and blocking resistance. [Means to solve the problem]

本發明者為了解決上述課題，提供滿足難燃性、抗滲出性及抗黏連性之全部的樹脂，而重複專心致力的研究。　　結果，發現只要是一種共聚物即可，其係包含來自含磷不飽和單體(A)的構成成分與來自聚合性不飽和單體(B)的構成成分之共聚物，前述來自(B)的構成成分包含來自具有碳原子數及氧原子數之合計為4～10的主鏈之不飽和羧酸單體(b-1)的構成成分，且相對於前述來自(A)的構成成分與前述來自(B)的構成成分之合計含量，來自具有碳數為1～4的烷基之(甲基)丙烯酸烷酯單體(b-2)的構成成分之含量為0.00～1.00質量%，而想出本發明。　　即，本發明之第一態樣為以下之共聚物。In order to solve the above-mentioned problems, the inventors of the present invention have repeated intensive studies to provide a resin that satisfies all of flame retardancy, bleed resistance, and blocking resistance. As a result, it was found that it is only necessary to be a copolymer, which is a copolymer comprising a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B), which is derived from (B) The constituents of the compound include constituents derived from the unsaturated carboxylic acid monomer (b-1) having a main chain having a total of 4 to 10 carbon atoms and oxygen atoms, and relative to the aforementioned constituents derived from (A) and The total content of the constituent components derived from the aforementioned (B) and the content of the constituent components derived from the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms are 0.00 to 1.00 mass %, and came up with the present invention. That is, the first aspect of the present invention is the following copolymer.

[1]一種共聚物，其係包含來自含磷不飽和單體(A)的構成成分與來自聚合性不飽和單體(B)的構成成分之共聚物，其特徵為：　　前述來自聚合性不飽和單體(B)的構成成分包含來自具有碳原子數及氧原子數之合計為4～10的主鏈之不飽和羧酸單體(b-1)的構成成分，且相對於前述來自含磷不飽和單體(A)的構成成分與前述來自聚合性不飽和單體(B)的構成成分之合計含量，來自具有碳數為1～4的烷基之(甲基)丙烯酸烷酯單體(b-2)的構成成分之含量為0.00～1.00質量%。[1] A copolymer comprising a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B), characterized in that: The constituent component of the saturated monomer (B) includes the constituent component derived from the unsaturated carboxylic acid monomer (b-1) having a main chain having a total of 4 to 10 carbon atoms and oxygen atoms, and is relative to the aforementioned constituent component derived from the unsaturated carboxylic acid monomer (b-1). The total content of the constituent components of the phosphorus unsaturated monomer (A) and the constituent components derived from the polymerizable unsaturated monomer (B) is derived from the alkyl (meth)acrylate monoester having an alkyl group having 1 to 4 carbon atoms. The content of the constituent components of the body (b-2) is 0.00 to 1.00 mass %.

上述[1]所述的共聚物亦較佳為具有以下之特徵的共聚物。下述之特徵亦可互相組合。The copolymer described in the above [1] is also preferably a copolymer having the following characteristics. The following features can also be combined with each other.

[2]如[1]記載之共聚物，其中前述來自含磷不飽和單體(A)的構成成分包含來自具有磷酸基與亞磷酸基的任一者之單體(a-1)的構成成分。　　[3]如[2]記載之共聚物，其中前述具有磷酸基與亞磷酸基的任一者之單體(a-1)為酸性・膦醯氧基聚氧化烯二醇單(甲基)丙烯酸酯。　　[4]如[1]～[3]中任一項記載之共聚物，其磷原子含量為0.1～10質量%。[2] The copolymer according to [1], wherein the constituent component derived from the phosphorus-containing unsaturated monomer (A) includes a structure derived from the monomer (a-1) having either a phosphoric acid group or a phosphorous acid group Element. [3] The copolymer according to [2], wherein the monomer (a-1) having either a phosphoric acid group or a phosphorous acid group is an acidic phosphonooxypolyoxyalkylene glycol mono(methyl) Acrylate. [4] The copolymer according to any one of [1] to [3], wherein the phosphorus atom content is 0.1 to 10 mass %.

[5]如[1]～[4]中任一項記載之共聚物，其中前述不飽和羧酸單體(b-1)係由丙烯酸、甲基丙烯酸、伊康酸、β-羧基乙基丙烯酸所選出的至少1種。　　[6]如[1]～[5]中任一項記載之共聚物，其中相對於前述來自含磷不飽和單體(A)的構成成分與前述來自聚合性不飽和單體(B)的構成成分之合計含量，前述來自不飽和羧酸單體(b-1)的構成成分之含量為30～95質量%。[5] The copolymer according to any one of [1] to [4], wherein the unsaturated carboxylic acid monomer (b-1) is composed of acrylic acid, methacrylic acid, itonic acid, β-carboxyethyl At least one selected from acrylic. [6] The copolymer according to any one of [1] to [5], wherein the constituent components derived from the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B)-derived As for the total content of the constituent components, the content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) is 30 to 95% by mass.

[7]如[1]～[6]中任一項記載之共聚物，其進一步包含來自鏈轉移劑(C)的構成成分。　　[8]如[7]記載之共聚物，其中前述鏈轉移劑(C)為巰基烷基羧酸酯(c-1)。　　[9]如[7]或[8]記載之共聚物，其中相對於前述來自含磷不飽和單體(A)的構成成分與前述來自聚合性不飽和單體(B)的構成成分之合計含量100質量份，前述來自鏈轉移劑(C)的構成成分之含量為0.1～10質量份。　　[10]如[1]～[9]中任一項記載之共聚物，其質量平均分子量為25000～70000。　　[11]如[1]～[10]中任一項記載之共聚物，其酸價為300～800mgKOH/g。[7] The copolymer according to any one of [1] to [6], which further contains a structural component derived from a chain transfer agent (C). [8] The copolymer according to [7], wherein the chain transfer agent (C) is a mercapto alkyl carboxylate (c-1). [9] The copolymer according to [7] or [8], which is relative to the sum of the constituent components derived from the phosphorus-containing unsaturated monomer (A) and the constituent components derived from the polymerizable unsaturated monomer (B) Content is 100 mass parts, and content of the said structural component derived from the chain transfer agent (C) is 0.1-10 mass parts. [10] The copolymer according to any one of [1] to [9], which has a mass-average molecular weight of 25,000 to 70,000. [11] The copolymer according to any one of [1] to [10], which has an acid value of 300 to 800 mgKOH/g.

本發明之第二態樣為以下之樹脂組成物。　　[12]一種樹脂組成物，其包含如[1]～[11]中任一項記載之共聚物。　　上述樹脂組成物亦較佳為具有以下之特徵的組成物。　　[13]如[12]記載之樹脂組成物，其進一步包含界面活性劑。　　本發明之第三態樣為以下之處理劑。　　[14]一種處理劑，其包含如[1]～[11]中任一項記載之共聚物。　　本發明之第四態樣為以下之加工品。　　[15]一種加工品，其具有基材與附著於前述基材上的如[1]～[11]中任一項記載之共聚物。　　上述加工品亦較佳為具有以下之特徵的組成物。　　[16]一種加工品，其係在基材上附著有如[14]記載之處理劑的固體成分之加工品，前述固體成分係對於前述加工品附著5～70質量%。 [發明的效果]The second aspect of the present invention is the following resin composition. [12] A resin composition comprising the copolymer according to any one of [1] to [11]. The above-mentioned resin composition is also preferably a composition having the following characteristics. [13] The resin composition according to [12], further comprising a surfactant. The third aspect of the present invention is the following treatment agent. [14] A treating agent comprising the copolymer according to any one of [1] to [11]. The fourth aspect of the present invention is the following processed product. [15] A processed product comprising a base material and the copolymer according to any one of [1] to [11] attached to the base material. The above-mentioned processed product is also preferably a composition having the following characteristics. [16] A processed product having a solid content of the treatment agent according to [14] adhered to a substrate, wherein the solid content is 5 to 70% by mass attached to the processed product. [Effect of invention]

本發明之共聚物係難燃性、抗滲出性及抗黏連性優異。　　又，使本發明之共聚物附著於基材上，藉此得到難燃性、抗滲出性及抗黏連性良好之加工品。　　本發明之樹脂組成物及處理劑，由於包含本發明之共聚物，可得到難燃性優異，抗滲出性及抗黏連性良好之塗膜。　　本發明之加工品具有基材與附著於前述基材上的本發明之共聚物。因此，具有優異的難燃性、抗滲出性及抗黏連性。 [實施發明的形態]The copolymer of the present invention is excellent in flame retardancy, exudation resistance and blocking resistance. In addition, by attaching the copolymer of the present invention to a substrate, a processed product having good flame retardancy, bleeding resistance and blocking resistance can be obtained. Since the resin composition and treatment agent of the present invention contain the copolymer of the present invention, a coating film with excellent flame retardancy, good bleed resistance and good blocking resistance can be obtained. The processed product of the present invention has a substrate and the copolymer of the present invention attached to the substrate. Therefore, it has excellent flame retardancy, exudation resistance and blocking resistance. [The form of carrying out the invention]

以下，詳細地說明本發明之共聚物、樹脂組成物、處理劑及加工品之較佳例。還有，本發明係不限定於僅以下所示的實施形態。例如，於不脫離本發明的宗旨之範圍內，種類、數、量、材料、構成等係可以追加、省略、變更。Hereinafter, preferred examples of the copolymer, resin composition, treatment agent, and processed product of the present invention will be described in detail. In addition, this invention is not limited only to embodiment shown below. For example, types, numbers, amounts, materials, structures, etc. can be added, omitted, or changed without departing from the gist of the present invention.

本說明書中的「～」係意指「～」的記載之前的值以上，且「～」的記載之後的值以下。　　又，本說明書中的「(甲基)丙烯酸酯」等之記載係與「丙烯酸酯及/或甲基丙烯酸酯」等同義。　　另外，本說明書中的「不飽和單體」等之記載係與「具有a,β-乙烯性不飽和基的單體」等同義。"-" in this specification means the value before the description of "-" or more and the value after the description of "-" or less. In addition, descriptions such as "(meth)acrylate" in this specification are synonymous with "acrylate and/or methacrylate" and the like. In addition, the description of "unsaturated monomer" and the like in this specification is synonymous with "monomer having an α,β-ethylenically unsaturated group" and the like.

[共聚物] 　　本實施形態之共聚物必須包含來自含磷不飽和單體(A)的構成成分(以下，亦稱為「來自(A)的構成成分」)與來自聚合性不飽和單體(B)的構成成分(以下，亦稱為「來自(B)的構成成分」)。惟，於來自(B)的構成成分中，不含來自(A)的構成成分。　　於共聚物中，來自含磷不飽和單體(A)的構成成分及來自聚合性不飽和單體(B)的構成成分皆為重複單位。於共聚物中，重複單位之排列順序係沒有特別的限制。即，共聚物可為無規共聚物、嵌段共聚物、交替共聚物之任一者。[Copolymer] The copolymer of the present embodiment must contain a constituent derived from the phosphorus-containing unsaturated monomer (A) (hereinafter, also referred to as "a constituent derived from (A)") and a polymerizable unsaturated monomer ( The constituents of B) (hereinafter, also referred to as "the constituents derived from (B)"). However, among the components derived from (B), the components derived from (A) are not included. In the copolymer, the constituents derived from the phosphorus-containing unsaturated monomer (A) and the constituents derived from the polymerizable unsaturated monomer (B) are both repeating units. In the copolymer, the arrangement order of the repeating units is not particularly limited. That is, the copolymer may be any of a random copolymer, a block copolymer, and an alternating copolymer.

＜含磷不飽和單體(A)＞　　共聚物中所包含之來自含磷不飽和單體(A)的構成成分係提高共聚物之難燃性。來自含磷不飽和單體(A)的構成成分係來自作為共聚物的原料使用之含磷不飽和單體(A)。　　作為共聚物的原料使用之含磷不飽和單體(A)係在分子中含有乙烯性不飽和鍵與磷原子者。<Phosphorus-containing unsaturated monomer (A)> The constituent component derived from the phosphorus-containing unsaturated monomer (A) contained in the copolymer improves the flame retardancy of the copolymer. The constituent component derived from the phosphorus-containing unsaturated monomer (A) is derived from the phosphorus-containing unsaturated monomer (A) used as a raw material of the copolymer. The phosphorus-containing unsaturated monomer (A) used as the raw material of the copolymer contains an ethylenically unsaturated bond and a phosphorus atom in the molecule.

作為含磷不飽和單體(A)之具體例，可舉出二甲基乙烯基膦酸酯、二乙基乙烯基膦酸酯、二苯基乙烯基膦酸酯、二苯基乙烯基膦酸酯、二甲基(1,2-二苯基-乙烯基)膦酸酯、二甲基-p-乙烯基苄基膦酸酯、二乙基-p-乙烯基苄基膦酸酯、二苯基-p-乙烯基苄基氧化膦、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物-10-p-乙烯基苄基、酸性・膦醯氧基乙基(甲基)丙烯酸酯、2-丙烯醯氧基乙基酸性磷酸酯、2-甲基丙烯醯氧基乙基酸性磷酸酯、二苯基-2-甲基丙烯醯氧基乙基磷酸酯、(甲基)丙烯醯基・氧基乙基酸性磷酸酯・單乙醇胺鹽、酸性・膦醯氧基聚氧乙烯二醇單(甲基)丙烯酸酯及酸性・膦醯氧基聚氧丙烯二醇二醇(甲基)丙烯酸酯以及此等之金屬鹽、銨鹽、胺鹽等。　　此等之化合物係可單獨或作為二種以上的混合物使用。Specific examples of the phosphorus-containing unsaturated monomer (A) include dimethylvinylphosphonate, diethylvinylphosphonate, diphenylvinylphosphonate, and diphenylvinylphosphine acid ester, dimethyl(1,2-diphenyl-vinyl)phosphonate, dimethyl-p-vinylbenzylphosphonate, diethyl-p-vinylbenzylphosphonate, Diphenyl-p-vinylbenzylphosphine oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-p-vinylbenzyl, acid phosphine oxide Ethyl (meth)acrylate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-methacryloyloxyethyl Phosphate ester, (meth)acryloyl/oxyethyl acid phosphoric acid ester/monoethanolamine salt, acid/phosphonooxypolyoxyethylene glycol mono(meth)acrylate and acid/phosphonooxypolyoxyethylene Propylene glycol glycol (meth)acrylates and their metal salts, ammonium salts, amine salts, and the like. These compounds can be used alone or as a mixture of two or more.

(具有磷酸基與亞磷酸基的任一者之單體(a-1)) 　　作為共聚物的原料使用之含磷不飽和單體(A)，較佳為具有下述式(1)所示的磷酸基與下述式(2)所示的亞磷酸基的任一者之單體(a-1)。藉由使用單體(a-1)，可得到難燃性更優異之共聚物。(Monomer (a-1) having either a phosphoric acid group or a phosphorous acid group) The phosphorus-containing unsaturated monomer (A) used as a raw material of the copolymer is preferably represented by the following formula (1) Monomer (a-1) of any one of the phosphoric acid group and the phosphorous acid group represented by the following formula (2). By using the monomer (a-1), a copolymer having more excellent flame retardancy can be obtained.

(式(1)中，＊表示與構成不飽和單體的原子之鍵結部)。

(In formula (1), * represents a bond with an atom constituting an unsaturated monomer).

(式(2)中，＊表示與構成不飽和單體的原子之鍵結部)。

(In formula (2), * represents a bond with an atom constituting an unsaturated monomer).

作為具有磷酸基與亞磷酸基的任一者之單體(a-1)，例如可舉出以通式(3)所示的化合物以及此化合物之金屬鹽、銨鹽及胺鹽等，可單獨或混合二種以上使用。Examples of the monomer (a-1) having either a phosphoric acid group or a phosphorous acid group include a compound represented by the general formula (3), and metal salts, ammonium salts, and amine salts of the compounds. Use alone or in combination of two or more.

(式(3)中，R¹ 及R² 各自獨立地表示氫原子或碳數1～3的烷基；Z表示氫原子或羥基；n為1～20之整數)。

(In formula (3), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Z represents a hydrogen atom or a hydroxyl group; and n is an integer of 1 to 20).

式(3)中，R¹ 及R² 各自獨立地表示氫原子或碳數1～3的烷基，較佳為氫原子或甲基。　　式(3)中，Z表示氫原子或羥基，較佳為氫原子。　　式(3)中，n為1～20之整數，較佳為1～8之整數，更佳為1～3之整數。In formula (3), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. In formula (3), Z represents a hydrogen atom or a hydroxyl group, preferably a hydrogen atom. In formula (3), n is an integer of 1-20, Preferably it is an integer of 1-8, More preferably, it is an integer of 1-3.

作為具有具有磷酸基與亞磷酸基的任一者之單體(a-1)的具體例，可舉出酸性・膦醯氧基聚氧化烯二醇單(甲基)丙烯酸酯。若具有磷酸基或亞磷酸基的單體(a-1)為酸性・膦醯氧基聚氧化烯二醇單(甲基)丙烯酸酯，則得到難燃性更高的共聚物故較宜。於酸性・膦醯氧基聚氧化烯二醇單(甲基)丙烯酸酯之中，尤其在每1分子的磷原子之比例高之點上，較佳為酸性・膦醯氧基乙基(甲基)丙烯酸酯。As a specific example of the monomer (a-1) which has any one of a phosphoric acid group and a phosphorous acid group, an acid phosphinodioxy polyoxyalkylene glycol mono(meth)acrylate is mentioned. If the monomer (a-1) having a phosphoric acid group or a phosphorous acid group is an acid phosphonooxypolyoxyalkylene glycol mono(meth)acrylate, it is preferable to obtain a copolymer having higher flame retardancy. Among the acid-phosphonooxypolyoxyalkylene glycol mono(meth)acrylates, especially in the point where the ratio of phosphorus atoms per molecule is high, acid-phosphonooxyethyl (methyl) is preferable. base) acrylate.

來自含磷不飽和單體(A)的構成成分之含量係可任意地選擇，但相對於來自(A)的構成成分與來自聚合性不飽和單體(B)的構成成分之合計含量，較佳為5～60質量%，更佳為7～50質量%，尤佳為10～40質量%。若相對於上述合計含量之來自(A)的構成成分之含量為5質量%以上，則成為難燃性更優異之共聚物。又，若相對於上述合計含量之來自(A)的構成成分之含量為60質量%以下，則可安定地聚合共聚物，同時共聚物之保存安定性變良好。另外，來自(A)的構成成分之含量為60質量%以下之共聚物係在將此使用作為加工品之材料時，抑制因來自(A)的構成成分之含量過多所造成的強度及耐熱黃變性之降低，同時可得到抗滲出性及抗黏連性良好之加工品。The content of the constituent components derived from the phosphorus-containing unsaturated monomer (A) can be arbitrarily selected, but the total content of the constituent components derived from the phosphorus-containing unsaturated monomer (A) and the constituent components derived from the polymerizable unsaturated monomer (B) is relatively small. 5-60 mass % is preferable, 7-50 mass % is more preferable, 10-40 mass % is especially preferable. If the content of the constituent component derived from (A) with respect to the total content is 5 mass % or more, the copolymer will be more excellent in flame retardancy. Moreover, when content of the structural component derived from (A) with respect to the said total content is 60 mass % or less, a copolymer can be polymerized stably, and the storage stability of a copolymer becomes favorable. In addition, when the content of the constituent component derived from (A) is 60 mass % or less, when this is used as the material of the processed product, the strength and heat-resistant yellow caused by the excessive content of the constituent component derived from (A) are suppressed. The denaturation is reduced, and the processed products with good anti-bleeding and anti-blocking properties can be obtained at the same time.

＜聚合性不飽和單體(B)＞　　共聚物中所包含之來自聚合性不飽和單體(B)的構成成分，係藉由與來自含磷不飽和單體(A)的構成成分併用，而提高共聚物之難燃性。又，來自聚合性不飽和單體(B)的構成成分係提高使用共聚物作為材料的加工品之密著性及外觀之安定性。來自聚合性不飽和單體(B)的構成成分係來自作為共聚物的原料使用之聚合性不飽和單體(B)。<Polymerizable unsaturated monomer (B)> The constituent component derived from the polymerizable unsaturated monomer (B) contained in the copolymer is used together with the constituent component derived from the phosphorus-containing unsaturated monomer (A), And improve the flame retardancy of the copolymer. In addition, the structural component derived from the polymerizable unsaturated monomer (B) improves the adhesion and appearance stability of the processed product using the copolymer as a material. The constituent component derived from the polymerizable unsaturated monomer (B) is derived from the polymerizable unsaturated monomer (B) used as a raw material of the copolymer.

共聚物中所包含之來自聚合性不飽和單體(B)的構成成分包含：具有碳原子數及氧原子數之合計為4～10的主鏈之不飽和羧酸單體(b-1)的構成成分。　　作為共聚物的原料使用之聚合性不飽和單體(B)，係可僅為不飽和羧酸單體(b-1)。又，聚合性不飽和單體(B)係除了不飽和羧酸單體(b-1)之外，還可包含在分子中具有乙烯性不飽和鍵，展現聚合性，與含磷不飽和單體(A)共聚合的其他不飽和單體。The constituent component derived from the polymerizable unsaturated monomer (B) contained in the copolymer includes: an unsaturated carboxylic acid monomer (b-1) having a main chain having a total of 4 to 10 carbon atoms and oxygen atoms constituents. The polymerizable unsaturated monomer (B) used as the raw material of the copolymer may be only the unsaturated carboxylic acid monomer (b-1). In addition to the unsaturated carboxylic acid monomer (b-1), the polymerizable unsaturated monomer (B) may contain an ethylenically unsaturated bond in the molecule, exhibit polymerizability, and interact with the phosphorus-containing unsaturated monolayer. Other unsaturated monomers copolymerized with body (A).

(具有碳原子數及氧原子數之合計為4～10的主鏈之不飽和羧酸單體(b-1)) 　　來自(B)的構成成分中所包含的具有碳原子數及氧原子數之合計為4～10的主鏈之不飽和羧酸單體(b-1)的構成成分，係提高共聚物之難燃性。來自(B)的構成成分係可僅一部分為上述之不飽和羧酸單體(b-1)的構成成分。若來自(B)的構成成分全部為不飽和羧酸單體(b-1)的構成成分，則成為難燃性更優異之共聚物故較宜。(Unsaturated carboxylic acid monomer (b-1) having a main chain in which the total number of carbon atoms and oxygen atoms is 4 to 10) The constituent components derived from (B) have carbon atoms and oxygen atoms The constituent components of the main chain unsaturated carboxylic acid monomer (b-1) whose total is 4 to 10 improve the flame retardancy of the copolymer. The constituents derived from (B) may be constituents of the above-mentioned unsaturated carboxylic acid monomer (b-1) only in part. When all the constituent components derived from (B) are the constituent components of the unsaturated carboxylic acid monomer (b-1), it is preferable to obtain a copolymer having more excellent flame retardancy.

作為共聚物的原料使用之不飽和羧酸單體(b-1)係具有碳原子數及氧原子數之合計為4～10的主鏈。所謂不飽和羧酸單體(b-1)的主鏈，就是指在化合物之結構中，由碳原子與氧原子所構成的分子鏈之中，最長的分子鏈。例如，主鏈的碳原子數與氧原子數之合計係於甲基丙烯酸中為4個，於馬來酸中成為6個。作為為共聚物的原料使用之不飽和羧酸單體為具有碳原子數及氧原子數之合計不超過10的主鏈者時，共聚物的難燃性變充分。又，使用具有碳原子數及氧原子數之合計不超過10的主鏈之不飽和羧酸單體作為共聚物的原料時，共聚物的聚合安定性變充分。The unsaturated carboxylic acid monomer (b-1) used as a raw material of the copolymer has a main chain having a total of 4 to 10 carbon atoms and oxygen atoms. The main chain of the unsaturated carboxylic acid monomer (b-1) refers to the longest molecular chain among the molecular chains composed of carbon atoms and oxygen atoms in the structure of the compound. For example, the total of the number of carbon atoms and the number of oxygen atoms in the main chain is 4 in methacrylic acid and 6 in maleic acid. When the unsaturated carboxylic acid monomer used as the raw material of the copolymer is one having a main chain in which the total number of carbon atoms and the number of oxygen atoms does not exceed 10, the flame retardancy of the copolymer becomes sufficient. In addition, when an unsaturated carboxylic acid monomer having a main chain in which the total number of carbon atoms and oxygen atoms does not exceed 10 is used as a raw material of the copolymer, the polymerization stability of the copolymer becomes sufficient.

作為不飽和羧酸單體(b-1)之具體例，可舉出丙烯酸、甲基丙烯酸、伊康酸、富馬酸、馬來酸及β-羧基乙基丙烯酸等。　　於此等之中，尤其因為可安定地聚合共聚物，提高共聚物中之不飽和羧酸單體(b-1)的構成成分之含量，較佳為丙烯酸、甲基丙烯酸或伊康酸，更佳為丙烯酸或甲基丙烯酸，尤佳為丙烯酸。Specific examples of the unsaturated carboxylic acid monomer (b-1) include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, β-carboxyethyl acrylic acid, and the like. Among them, especially since the copolymer can be stably polymerized, the content of the constituent components of the unsaturated carboxylic acid monomer (b-1) in the copolymer is increased, and acrylic acid, methacrylic acid or itonic acid is preferred, More preferred is acrylic acid or methacrylic acid, and particularly preferred is acrylic acid.

來自不飽和羧酸單體(b-1)的構成成分之含量係可任意地選擇，但相對於共聚物中之來自(A)的構成成分與來自(B)的構成成分之合計含量，較佳為30質量%～95質量%。相對於上述合計含量，來自不飽和羧酸單體(b-1)的構成成分之含量的下限值更佳為35質量%以上，尤佳為40質量%以上。相對於上述合計含量，來自不飽和羧酸單體(b-1)的構成成分之含量的上限值更佳為90質量%以下，尤佳為85質量%以下。若上述來自不飽和羧酸單體(b-1)的構成成分之含量為30質量%以上，則可安定地聚合共聚物(P)。若上述之來自不飽和羧酸單體(b-1)的構成成分之含量為95質量%以下，則成為難燃性更優異的共聚物。The content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) can be arbitrarily selected, but is less than the total content of the constituent components derived from (A) and the constituent components derived from (B) in the copolymer. Preferably it is 30 mass % - 95 mass %. The lower limit of the content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) is more preferably 35% by mass or more, and particularly preferably 40% by mass or more, relative to the total content. The upper limit of the content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) is more preferably 90% by mass or less, and particularly preferably 85% by mass or less, relative to the total content. The copolymer (P) can be stably polymerized when the content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) is 30% by mass or more. When the content of the constituent components derived from the above-mentioned unsaturated carboxylic acid monomer (b-1) is 95% by mass or less, a copolymer having more excellent flame retardancy will be obtained.

(具有碳數為1～4的烷基之(甲基)丙烯酸烷酯單體(b-2)) 　　於本實施形態中，相對於來自(A)的構成成分與來自(B)的構成成分之合計含量，必須使來自具有碳數為1～4的烷基之(甲基)丙烯酸烷酯單體(b-2)的構成成分之含量(包含不含有之情況)成為0.00～1.00質量%。　　作為共聚物的原料使用之具有碳數為1～4的烷基之(甲基)丙烯酸烷酯單體(b-2)，可舉出下述式(4)所示的單體。(Alkyl (meth)acrylate monomer (b-2) having an alkyl group having a carbon number of 1 to 4) The total content must be 0.00 to 1.00 mass % of the constituent components derived from the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms (b-2). . The alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms used as a raw material of the copolymer includes a monomer represented by the following formula (4).

(式(4)中，R³ ～R⁵ 各自獨立地表示氫原子或甲基；R⁶ 係碳數為1～4之直鏈或分枝的烷基)。

(In formula (4), R ³ to R ⁵ each independently represent a hydrogen atom or a methyl group; R ⁶ is a linear or branched alkyl group having 1 to 4 carbon atoms).

作為以式(4)所示的(甲基)丙烯酸烷酯單體(b-2)之具體例，可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯等。Specific examples of the alkyl (meth)acrylate monomer (b-2) represented by the formula (4) include methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl) Propyl acrylate, butyl (meth)acrylate, etc.

相對於來自(A)的構成成分與來自(B)的構成成分之合計含量，來自具有碳數為1～4的烷基之(甲基)丙烯酸烷酯單體(b-2)的構成成分之含量為0.00～1.00質量%。來自(甲基)丙烯酸烷酯單體(b-2)的構成成分之含量更佳為0.75質量%以下，尤佳為0.50質量%以下。若來自(甲基)丙烯酸烷酯單體(b-2)的構成成分之含量超過1.00質量%，則共聚物之難燃性降低。Structural component derived from the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms with respect to the total content of the structural component derived from (A) and the structural component derived from (B) The content is 0.00 to 1.00 mass %. The content of the constituent components derived from the alkyl (meth)acrylate monomer (b-2) is more preferably 0.75 mass % or less, particularly preferably 0.50 mass % or less. When content of the structural component derived from the alkyl (meth)acrylate monomer (b-2) exceeds 1.00 mass %, the flame retardance of a copolymer will fall.

於來自聚合性不飽和單體(B)的構成成分中，亦可包含不是來自不飽和羧酸單體(b-1)及具有碳數為1～4的烷基之(甲基)丙烯酸烷酯單體(b-2)的構成成分之來自其他不飽和單體的構成成分。　　作為可作為共聚物的原料使用之(b-1)、(b-2)以外的聚合性不飽和單體，例如可舉出(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸烯丙酯、乙二醇二(甲基)丙烯酸酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、乙二醇單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、聚四亞甲基二醇單(甲基)丙烯酸酯、聚乙二醇聚四亞甲基二醇單(甲基)丙烯酸酯、聚丙二醇聚四亞甲基二醇單(甲基)丙烯酸酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸甲基環氧丙酯、(甲基)丙烯酸3,4-環氧基環己基甲酯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二羥甲基三環癸烷二(甲基)丙烯酸酯、(甲基)丙烯酸異冰片酯、苯氧基聚乙二醇(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯等之(甲基)丙烯酸酯；富馬二甲酸酯、富馬酸二乙酯、富馬酸二丁酯、富馬酸二-(2-乙基己基)酯等之富馬酸酯；馬來酸二甲酯、馬來酸二乙酯、馬來酸二丁酯、馬來酸二-(2-乙基己基)酯等之馬來酸酯；甲基丙烯醯胺；N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺等之(甲基)丙烯醯胺衍生物；甲氧基苯乙烯、乙氧基苯乙烯乙烯基苯甲酸、乙烯基苯甲酸甲酯、乙烯基苄基乙酸酯、羥基苯乙烯、二乙烯基苯等之苯乙烯衍生物；乙酸乙烯酯；丙酸乙烯酯、己酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯等之乙烯酯類；甲基馬來醯亞胺、乙基馬來醯亞胺、異丙基馬來醯亞胺、環己基馬來醯亞胺、苯基馬來醯亞胺、苄基馬來醯亞胺、萘基馬來醯亞胺等之N取代馬來醯亞胺化合物；伊康酸單甲酯、伊康酸二甲酯、伊康酸單乙酯、伊康酸二乙酯、伊康酸單丁酯、伊康酸二丁酯等之伊康酸酯；巴豆酸甲酯、巴豆酸乙酯、巴豆酸丁酯等之巴豆酸酯；鄰苯二甲酸二甲酯、鄰苯二甲酸二乙酯、鄰苯二甲酸二丙酯、鄰苯二甲酸二丁酯、鄰苯二甲酸二己酯等之鄰苯二甲酸酯；2-丙烯醯氧基乙基-琥珀酸等之琥珀酸酯等，此等係可單獨或組合二種以上使用。In the structural component derived from the polymerizable unsaturated monomer (B), the alkane (meth)acrylate which is not derived from the unsaturated carboxylic acid monomer (b-1) and the alkyl group having 1 to 4 carbon atoms may be included Among the constituents of the ester monomer (b-2) are constituents derived from other unsaturated monomers. Examples of polymerizable unsaturated monomers other than (b-1) and (b-2) that can be used as raw materials for copolymers include amyl (meth)acrylate, hexyl (meth)acrylate, ( 2-ethylhexyl (meth)acrylate, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, methoxyethyl (meth)acrylate, butoxy (meth)acrylate ethyl ester, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylate ) hydroxybutyl acrylate, ethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate ) acrylate, polyethylene glycol polytetramethylene glycol mono(meth)acrylate, polypropylene glycol polytetramethylene glycol mono(meth)acrylate, glycidyl (meth)acrylate, Methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butyl Glycol di(meth)acrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate Meth)acrylate, Dimethyloltricyclodecane di(meth)acrylate, Isobornyl (meth)acrylate, Phenoxy polyethylene glycol (meth)acrylate, Pentaerythritol tetrakis(meth)acrylate ) (meth)acrylate of acrylate, etc.; fumarate of fumarate, diethyl fumarate, dibutyl fumarate, di-(2-ethylhexyl) fumarate, etc. acid esters; maleic acid esters of dimethyl maleate, diethyl maleate, dibutyl maleate, bis-(2-ethylhexyl) maleate, etc.; methacrylic acid amide; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (meth) acrylamide, etc. ( Methyl) acrylamide derivatives; methoxy styrene, ethoxy styrene vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, divinyl benzene, etc. Styrene derivatives; vinyl acetate; vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, etc. vinyl esters; methylmaleimide, ethyl N-substituted maleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide, etc. Maleimide compounds; Iconic acid monomethyl ester, Iconic acid dimethyl ester, Iconic acid monoethyl ester, Iconic acid diethyl ester, Iconic acid monobutyl ester, Iconic acid dibutyl ester, etc. Iconic acid esters; crotonic acid esters of methyl crotonate, ethyl crotonate, butyl crotonate, etc.; dimethyl phthalate, diethyl phthalate, dipropyl phthalate, ortho Phthalates such as dibutyl phthalate, dihexyl phthalate, etc.; succinates such as 2-acryloyloxyethyl-succinic acid, etc. These can be used alone or in combination of two Use above.

來自聚合性不飽和單體(B)的構成成分之含量係可任意地選擇，但相對於來自(A)的構成成分與來自(B)的構成成分之合計含量，較佳為40質量%～95質量%。　　相對於上述合計含量之來自(B)的構成成分之含量的下限值更佳為50質量%以上，尤佳為60質量%以上。相對於上述合計含量之來自(B)的構成成分之含量的上限值更佳為90質量%以下，尤佳為85質量%以下。若相對於上述合計含量之來自(B)的構成成分之含量為40質量%以上，則可安定地聚合共聚物。又，若相對於上述合計含量之來自(B)的構成成分之含量為95質量%以下，則由於來自(A)的構成成分與來自(B)的構成成分之相乘效果變更顯著，共聚物的難燃性更進一步升高。The content of the structural component derived from the polymerizable unsaturated monomer (B) can be arbitrarily selected, but is preferably 40% by mass to the total content of the structural component derived from (A) and the structural component derived from (B). 95% by mass. The lower limit of the content of the constituent components derived from (B) with respect to the total content is more preferably 50 mass % or more, and particularly preferably 60 mass % or more. The upper limit of the content of the constituent components derived from (B) with respect to the total content is more preferably 90% by mass or less, and particularly preferably 85% by mass or less. The copolymer can be stably polymerized when the content of the constituent component derived from (B) is 40% by mass or more with respect to the total content. In addition, when the content of the constituent components derived from (B) with respect to the above-mentioned total content is 95% by mass or less, the synergistic effect of the constituent components derived from (A) and the constituent components derived from (B) changes remarkably, and the copolymer The flame retardancy is further increased.

＜鏈轉移劑(C)＞　　本實施形態之共聚物係可含有來自鏈轉移劑(C)的構成成分。來自鏈轉移劑(C)的構成成分，係為了調整包含來自含磷不飽和單體(A)的構成成分與來自聚合性不飽和單體(B)的構成成分之共聚物的質量平均分子量，在聚合時所使用之鏈轉移劑(C)的片段係鍵結於共聚物。<Chain transfer agent (C)> The copolymer of the present embodiment may contain constituent components derived from the chain transfer agent (C). The structural component derived from the chain transfer agent (C) is to adjust the mass average molecular weight of the copolymer containing the structural component derived from the phosphorus-containing unsaturated monomer (A) and the structural component derived from the polymerizable unsaturated monomer (B), The segment of the chain transfer agent (C) used in the polymerization is bound to the copolymer.

作為鏈轉移劑(C)，例如可舉出硫二甘醇、乙烯硫乙醇、二正丁基硫化物、二正辛基硫化物、二苯基硫化物、二異丙基硫化物、巰基乙酸、巰基丙酸、巰基丁酸、巰基己酸、巰基乙酸2-乙基己酯、巰基琥珀酸、硫代乙酸、硫脲等之含硫化合物；亞硫酸氫鹽、次磷酸及其鹽以及亞磷酸及其鹽等之含磷化合物；甲醛、乙醛、丙醛等之醛化合物；甲酸、甲酸鈉、甲酸銨等之有機酸；異丙醇等之醇化合物等。此等之鏈轉移劑(C)係可單獨或組合二種以上使用。　　還有，在來自鏈轉移劑(C)的構成成分亦為來自含磷不飽和單體(A)的構成成分時，視為來自含磷不飽和單體(A)的構成成分。Examples of the chain transfer agent (C) include thiodiglycol, ethylene thioethanol, di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, diisopropyl sulfide, and thioglycolic acid. , mercaptopropionic acid, mercaptobutyric acid, mercaptocaproic acid, 2-ethylhexyl thioglycolate, mercaptosuccinic acid, thioacetic acid, thiourea and other sulfur-containing compounds; bisulfite, hypophosphorous acid and its salts and sulfites Phosphorus-containing compounds such as phosphoric acid and its salts; aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, etc.; organic acids such as formic acid, sodium formate, ammonium formate, etc.; alcohol compounds such as isopropanol, etc. These chain transfer agents (C) can be used alone or in combination of two or more. In addition, when the structural component derived from the chain transfer agent (C) is also a structural component derived from the phosphorus-containing unsaturated monomer (A), it is regarded as a structural component derived from the phosphorus-containing unsaturated monomer (A).

作為鏈轉移劑(C)，於上述之中，尤其從聚合安定性，及來自聚合性不飽和單體(B)的構成成分中的末端羧酸與來自含磷不飽和單體(A)的構成成分之相乘效果所致的難燃性升高之觀點來看，較佳為包含巰基烷基羧酸酯。作為巰基烷基羧酸酯，可舉出巰基乙酸、巰基丙酸、巰基丁酸、巰基己酸等。As the chain transfer agent (C), among the above, in particular, the polymerization stability, and the terminal carboxylic acid in the constituent components of the polymerizable unsaturated monomer (B) and the phosphorus-containing unsaturated monomer (A) are derived. From the viewpoint of the improvement in flame retardancy due to the synergistic effect of the constituent components, it is preferable to contain a mercapto alkyl carboxylate. As a mercaptoalkyl carboxylate, mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptocaproic acid, etc. are mentioned.

來自鏈轉移劑(C)的構成成分之含量係可任意地選擇，但相對於來自(A)的構成成分與來自(B)的構成成分之合計含量100質量份，較佳為0.1～10質量份。　　相對於上述合計含量，來自鏈轉移劑(C)的構成成分之含量的下限值更佳為1質量份以上，尤佳為2質量份以上。相對於上述合計含量，來自鏈轉移劑(C)的構成成分之含量的上限值更佳為9質量份以下，尤佳為8質量份以下。相對於上述合計含量，若來自鏈轉移劑(C)的構成成分之含量為0.1質量份以上，則因鏈轉移劑(C)調整所具有的共聚物之質量平均分子量的效果，而成為具有優異的聚合安定性及保存安定性之共聚物。又，相對於上述合計含量，若來自鏈轉移劑(C)的構成成分之含量為10質量份以下，則來自鏈轉移劑(C)的構成成分係不妨礙共聚物的難燃性，而成為難燃性更優異者。來自鏈轉移劑(C)的構成成分之含量係可用¹ H-NMR等眾所周知之方法測定。又，為了使來自鏈轉移劑(C)的構成成分之含量成為上述範圍，較佳為將比含量稍多的量使用於聚合時。The content of the structural component derived from the chain transfer agent (C) can be arbitrarily selected, but is preferably 0.1 to 10 mass parts relative to 100 parts by mass of the total content of the structural component derived from (A) and the structural component derived from (B). share. The lower limit value of the content of the constituent components derived from the chain transfer agent (C) is more preferably 1 part by mass or more, particularly preferably 2 parts by mass or more, with respect to the total content. The upper limit of the content of the constituent components derived from the chain transfer agent (C) is more preferably 9 parts by mass or less, particularly preferably 8 parts by mass or less, with respect to the total content. When the content of the constituent components derived from the chain transfer agent (C) is 0.1 part by mass or more with respect to the above-mentioned total content, the chain transfer agent (C) has an effect of adjusting the mass average molecular weight of the copolymer, which is excellent. The polymer stability and storage stability of the copolymer. In addition, when the content of the constituent components derived from the chain transfer agent (C) is 10 parts by mass or less relative to the above-mentioned total content, the constituent components derived from the chain transfer agent (C) do not interfere with the flame retardancy of the copolymer and become Those with better flame retardancy. The content of the constituent components derived from the chain transfer agent (C) can be measured by a well-known method such as ¹ H-NMR. Moreover, in order to make content of the structural component originating in a chain transfer agent (C) into the said range, it is preferable to use a slightly larger quantity than content at the time of superposition|polymerization.

「質量平均分子量」　　本實施形態之共聚物係質量平均分子量較佳為25000～70000。質量平均分子量之下限值更佳為27000以上，尤佳為30000以上。質量平均分子量之上限值更佳為60000以下，尤佳為55000以下。若共聚物之質量平均分子量為25000以上，則共聚物成為難燃性更優異者。若共聚物之質量平均分子量為70000以下，則共聚物之聚合安定性變良好。"Mass average molecular weight" The mass average molecular weight of the copolymer of the present embodiment is preferably 25,000 to 70,000. The lower limit value of the mass average molecular weight is more preferably 27,000 or more, particularly preferably 30,000 or more. The upper limit value of the mass average molecular weight is more preferably 60,000 or less, particularly preferably 55,000 or less. When the mass average molecular weight of the copolymer is 25,000 or more, the copolymer is more excellent in flame retardancy. When the mass average molecular weight of the copolymer is 70,000 or less, the polymerization stability of the copolymer becomes good.

共聚物之質量平均分子量係使用凝膠滲透層析術(GPC)商品名「Shodex GPC-101」(昭和電工股份有限公司製，「Shodex」為註冊商標)，如以下地測定之值。　　調製於磷酸氫二鈉12水合物34.5g及磷酸二氫鈉2水合物46.2g中，加入超純水而使全量成為5.000g之水溶液，作為載液。於此載液中溶解共聚物，使用泵(＜DU-H2000＞，Shodex製)，以流速0.5ml/min.進行測定。　　管柱係使用水系GPC管柱(分析管柱：＜OHpak SB-806M MQ＞，Shodex製，參考管柱：＜OHpak SB-800RL＞，Shodex製)。使用RI檢測器(＜RI-71S＞，Shodex製)作為檢測器，使用聚丙烯酸鈉(Sigma-Aldrich)作為分子量標準樣品。The mass average molecular weight of the copolymer was measured as follows using gel permeation chromatography (GPC) trade name "Shodex GPC-101" (manufactured by Showa Denko Co., Ltd., "Shodex" is a registered trademark). Prepared in 34.5 g of disodium hydrogen phosphate 12 hydrate and 46.2 g of sodium dihydrogen phosphate dihydrate, and added ultrapure water to make the total amount an aqueous solution of 5.000 g as a carrier liquid. The copolymer was dissolved in this carrier liquid, and the measurement was performed at a flow rate of 0.5 ml/min. using a pump (<DU-H2000>, manufactured by Shodex). As the column, an aqueous GPC column (analytical column: <OHpak SB-806M MQ>, manufactured by Shodex, reference column: <OHpak SB-800RL>, manufactured by Shodex) was used. An RI detector (<RI-71S>, manufactured by Shodex) was used as a detector, and sodium polyacrylate (Sigma-Aldrich) was used as a molecular weight standard sample.

「酸價」　　本實施形態之共聚物係酸價較佳為300～800mgKOH/g。酸價之下限值較佳為350mgKOH/g以上，更佳為450mgKOH/g以上。酸價之上限值較佳為785mgKOH/g以下，更佳為750mgKOH/g以下。若共聚物之酸價為300mgKOH/g以上，則共聚物成為難燃性更優異者。若共聚物之酸價為800mgKOH/g以下，則共聚物之聚合安定性及保存安定性變良好"Acid value" The acid value of the copolymer of the present embodiment is preferably 300 to 800 mgKOH/g. The lower limit value of the acid value is preferably 350 mgKOH/g or more, more preferably 450 mgKOH/g or more. The upper limit of the acid value is preferably 785 mgKOH/g or less, more preferably 750 mgKOH/g or less. When the acid value of the copolymer is 300 mgKOH/g or more, the copolymer is more excellent in flame retardancy. When the acid value of the copolymer is 800 mgKOH/g or less, the polymerization stability and storage stability of the copolymer are improved.

「磷原子含量」　　共聚物中的磷原子含量係可任意地選擇，但較佳為0.1～10質量%。上述的磷原子含量之下限值更佳為0.5質量%以上，尤佳為1.0質量%以上。上述的磷原子含量之上限值更佳為9.0質量%以下，尤佳為8.0質量%以下。若上述的磷原子含量為0.1質量%以上，則成為難燃性更優異的共聚物。若上述的磷原子含量為10質量%以下，則可安定地聚合共聚物，同時共聚物的保存安定性變良好。又，若上述的磷原子含量為10質量%以下，則在使用此作為加工品的材料時，抑制因磷原子含量過多所造成的對基材的密著性降低及外觀變化，同時可得到抗滲出性及抗黏連性良好的加工品。"Phosphorus Atom Content" The phosphorus atom content in the copolymer can be arbitrarily selected, but is preferably 0.1 to 10% by mass. The lower limit value of the above-mentioned phosphorus atom content is more preferably 0.5 mass % or more, particularly preferably 1.0 mass % or more. The upper limit value of the above-mentioned phosphorus atom content is more preferably 9.0 mass % or less, and particularly preferably 8.0 mass % or less. When the above-mentioned phosphorus atom content is 0.1 mass % or more, a copolymer having more excellent flame retardancy will be obtained. When the above-mentioned phosphorus atom content is 10 mass % or less, the copolymer can be stably polymerized, and the storage stability of the copolymer is improved. In addition, when the above-mentioned phosphorus atom content is 10 mass % or less, when this is used as a material of a processed product, the decrease in adhesion to the base material and the appearance change due to the excessive phosphorus atom content can be suppressed, and the anti-aging can be obtained. Processed product with good bleed and anti-blocking properties.

[共聚物之製造方法] 　　本實施形態之共聚物例如可藉由使用以往習知的方法，將共聚物之原料的不飽和單體予以自由基共聚合而製造。　　原料的不飽和單體包含上述之含磷不飽和單體(A)與聚合性不飽和單體(B)。[Production Method of Copolymer] The copolymer of the present embodiment can be produced by, for example, using a conventionally known method to radically copolymerize an unsaturated monomer as a raw material of the copolymer. The unsaturated monomer of the raw material includes the above-mentioned phosphorus-containing unsaturated monomer (A) and polymerizable unsaturated monomer (B).

作為將不飽和單體共聚合之方法，例如可使用懸浮聚合法、乳化聚合法、溶液聚合法、塊狀聚合法等。又，可使用連續式聚合法，也可使用分批式聚合法。　　在將不飽和單體共聚合而製造共聚物時，視需要可使用鏈轉移劑(C)、以下所示的溶劑、界面活性劑、起始劑、中和劑。As a method for copolymerizing the unsaturated monomer, for example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, a bulk polymerization method, or the like can be used. In addition, a continuous polymerization method or a batch polymerization method may be used. When producing a copolymer by copolymerizing an unsaturated monomer, a chain transfer agent (C), a solvent shown below, a surfactant, an initiator, and a neutralizing agent can be used as necessary.

作為製造共聚物之方法，較佳為使用採用界面活性劑的乳化聚合法或不用界面活性劑的溶液聚合法。　　於乳化聚合法中，首先混合原料的不飽和單體、溶劑、界面活性劑(乳化劑)與上述的鏈轉移劑(C)而成為單體乳化物。鏈轉移劑(C)係視需要使用者，亦可不含於單體乳化物中。其次，混合所得之單體乳化物與起始劑，使其在指定的反應溫度下反應，成為在溶劑中分散有共聚物的樹脂組成物(水性乳液)。於樹脂組成物中，共聚物的一部分亦可溶解於溶劑中。其後，視需要將中和劑加到樹脂組成物中而中和。然後，藉由去除樹脂組成物中的溶劑而使其乾燥，可從樹脂組成物中，分離包含共聚物的樹脂固體成分。As a method for producing the copolymer, it is preferable to use an emulsion polymerization method using a surfactant or a solution polymerization method not using a surfactant. In the emulsion polymerization method, the unsaturated monomer, solvent, surfactant (emulsifier) and the above-mentioned chain transfer agent (C) of the raw materials are first mixed to form a monomer emulsion. The chain transfer agent (C) may be used as needed, and may not be included in the monomer emulsion. Next, the obtained monomer emulsion and the initiator are mixed and reacted at a predetermined reaction temperature to obtain a resin composition (aqueous emulsion) in which the copolymer is dispersed in a solvent. In the resin composition, a part of the copolymer may be dissolved in the solvent. Thereafter, a neutralizing agent is added to the resin composition for neutralization as necessary. Then, by removing the solvent in the resin composition and drying it, the resin solid content including the copolymer can be separated from the resin composition.

於溶液聚合法中，首先混合原料的不飽和單體、溶劑與上述的鏈轉移劑(C)而成為單體溶液。鏈轉移劑(C)係視需要使用者，亦可不含於單體溶液中。其次，混合所得之單體溶液與起始劑，使其在指定的反應溫度反應，成為在溶劑中溶解有共聚物的樹脂組成物。於樹脂組成物中，亦可藉由共聚物的高分子量化等，而共聚物的一部分不溶解於溶劑。其後，視需要將中和劑加到樹脂組成物而進行中和。然後，藉由去除樹脂組成物中的溶劑而使其乾燥，可從樹脂組成物中，分離包含共聚物的樹脂固體成分。In the solution polymerization method, first, the unsaturated monomer, the solvent, and the above-mentioned chain transfer agent (C) of the raw materials are mixed to obtain a monomer solution. The chain transfer agent (C) may be used as needed, and may not be included in the monomer solution. Next, the obtained monomer solution and the initiator are mixed and reacted at a predetermined reaction temperature to obtain a resin composition in which the copolymer is dissolved in a solvent. In the resin composition, a part of the copolymer may not be dissolved in the solvent due to the high molecular weight of the copolymer or the like. Thereafter, neutralization is performed by adding a neutralizing agent to the resin composition as necessary. Then, by removing the solvent in the resin composition and drying it, the resin solid content including the copolymer can be separated from the resin composition.

於乳化聚合法(或溶液聚合法)中，作為混合單體乳化物(溶液聚合法中為單體溶液)與起始劑之方法，可使用以往習知的方法。　　例如，於起始劑中，可使用滴下單體乳化物(溶液聚合法中為單體溶液)而添加，進行攪拌之方法。此時，可將起始劑的一部分與單體乳化物(溶液聚合法中為單體溶液)一起滴下至起始劑中。又，也可使用一併混合起始劑之全量與單體乳化物(溶液聚合法中的單體溶液)的全量之方法。In the emulsion polymerization method (or the solution polymerization method), a conventionally known method can be used as the method of mixing the monomer emulsion (monomer solution in the solution polymerization method) and the initiator. For example, a monomer emulsion (monomer solution in the solution polymerization method) can be added dropwise to the starter, followed by stirring. At this time, a part of the initiator may be dropped into the initiator together with the monomer emulsion (monomer solution in the solution polymerization method). Moreover, the method of mixing together the whole quantity of an initiator and the whole quantity of a monomer emulsion (monomer solution in a solution polymerization method) can also be used.

於本實施形態的共聚物之製造方法中，作為調整共聚物之質量平均分子量之方法，並沒有特別得限定，例如可舉出使用鏈轉移劑(C)之方法，或調整起始劑的濃度之方法、調整反應溫度之方法等。反應溫度係可按照起始劑的種類等而變更。In the method for producing the copolymer of the present embodiment, the method for adjusting the mass average molecular weight of the copolymer is not particularly limited. For example, a method of using a chain transfer agent (C), or adjusting the concentration of the initiator method, the method of adjusting the reaction temperature, etc. The reaction temperature can be changed according to the type of the starting agent and the like.

＜溶劑＞　　作為在製造共聚物時所用之溶劑，可任意地選擇，例如可使用水等之水性溶劑或通常使用的有機溶劑等，較佳為水性溶劑。<Solvent> The solvent used in the production of the copolymer can be arbitrarily selected. For example, an aqueous solvent such as water or a commonly used organic solvent can be used, and an aqueous solvent is preferred.

作為溶劑，例如可舉出水、甲醇、乙醇、丙醇、異丙醇、丁醇等之醇類；乙酸乙類、乙酸異丙類、溶纖劑乙酸酯、丁基溶纖劑乙酸酯等之乙二醇單烷基醚乙酸酯類；二乙二醇單甲基醚乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯等之二乙二醇單烷基醚乙酸酯類；丙二醇單烷基醚乙酸酯類、二丙二醇單烷基醚乙酸酯類等之乙酸酯類；乙二醇二烷基醚類；甲基卡必醇、乙基卡必醇、丁基卡必醇等之二乙二醇二烷基醚類；三乙二醇二烷基醚類；丙二醇二烷基醚類；二丙二醇二烷基醚類；甲醚、***、1,4-二

烷、四氫呋喃等之醚類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等之酮類；苯、甲苯、二甲苯、己烷、辛烷、癸烷等之烴類；石油醚、石油腦、氫化石油腦、溶劑油等之石油系溶劑；乳酸甲酯、乳酸乙酯、乳酸丁酯等之乳酸酯類；二甲基甲醯胺、N-甲基吡咯啶酮、二乙二醇單乙基醚等。此等之溶劑係可單獨或組合二種以上使用。Examples of the solvent include alcohols such as water, methanol, ethanol, propanol, isopropanol, butanol; ethyl acetate, isopropyl acetate, cellosolve acetate, butyl cellosolve acetate, and the like ethylene glycol monoalkyl ether acetates; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate, etc. Esters; propylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ether acetates, etc. acetates; ethylene glycol dialkyl ethers; methyl carbitol, ethyl carbitol, butyl Diethylene glycol dialkyl ethers such as carbitol; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; methyl ether, diethyl ether, 1,4-dialkyl ether

Ethers such as alkane, tetrahydrofuran, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; hydrocarbons such as benzene, toluene, xylene, hexane, octane, decane, etc. ; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, mineral spirits, etc.; lactic acid esters such as methyl lactate, ethyl lactate, butyl lactate, etc.; dimethylformamide, N-methylpyrrolidone , Diethylene glycol monoethyl ether, etc. These solvent systems can be used individually or in combination of 2 or more types.

＜起始劑＞　　藉由自由基聚合，使原料的不飽和單體共聚合而製造共聚物時，在起始劑之存在下共聚合。<Initiator> When a copolymer is produced by copolymerizing the unsaturated monomer of the raw material by radical polymerization, the copolymer is carried out in the presence of an initiator.

作為起始劑，只要能開始自由基聚合者，則沒有特別的限定，可使用通常使用的過氧化物或偶氮化合物等。　　作為起始劑之具體例，可舉出過硫酸鈉、過硫酸鉀、過硫酸銨、過氧化氫、苯甲醯基過氧化物、二異丙苯基過氧化物、二異丙基過氧化物、二第三丁基過氧化物、第三丁基過氧苯甲酸酯、第三己基過氧苯甲酸酯、第三丁基過氧-2-乙基己酸酯、第三己基過氧-2-乙基己酸酯、1,1-雙(第三丁基過氧)-3,3,5-三甲基環己烷、2,5-二甲基-2,5-雙(第三丁基過氧)己基-3,3-異丙基氫過氧化物、第三丁基氫過氧化物、二異丙苯基氫過氧化物、乙醯基過氧化物、雙(4-第三丁基環己基)過氧二碳酸酯、二異丙基過氧二碳酸酯、異丁基過氧化物、3,3,5-三甲基己醯基過氧化物、月桂基過氧化物、1,1-雙(第三己基過氧)-3,3,5-三甲基環己烷、偶氮雙異丁腈、偶氮雙甲醯胺等依照反應亦可使用適當的還原劑。The initiator is not particularly limited as long as it can initiate radical polymerization, and generally used peroxides, azo compounds, and the like can be used. Specific examples of the initiator include sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, benzyl peroxide, dicumyl peroxide, diisopropyl peroxide compound, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tertiary hexyl Peroxy-2-ethylhexanoate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5- Bis(tert-butylperoxy)hexyl-3,3-isopropyl hydroperoxide, tert-butyl hydroperoxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl Base peroxide, 1,1-bis(3rd-hexylperoxy)-3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobisformamide, etc. can also be used according to the reaction appropriate reducing agent.

起始劑之使用量係可任意地選擇，但為了成為適當的聚合速度，相對於原料的含磷不飽和單體(A)與聚合性不飽和單體(B)之合計100質量份，較佳為0.01～20質量份，更佳為0.1～15質量份，尤佳為0.5～10質量份。The usage-amount of the initiator can be arbitrarily selected, but in order to achieve an appropriate polymerization rate, it is more 0.01-20 mass parts is preferable, 0.1-15 mass parts is more preferable, 0.5-10 mass parts is especially preferable.

＜界面活性劑＞　　界面活性劑係使用於藉由乳化聚合法製造共聚物時。　　作為界面活性劑，可使用一般市售的陰離子性界面活性劑、非離子性界面活性劑、陽離子性界面活性劑及共聚合性界面活性劑。於此等之中，作為界面活性劑，較佳為使用陰離子性界面活性劑及非離子性界面活性劑。<Surfactant> Surfactant is used when the copolymer is produced by the emulsion polymerization method. As the surfactant, generally commercially available anionic surfactants, nonionic surfactants, cationic surfactants and copolymerizable surfactants can be used. Among these, it is preferable to use an anionic surfactant and a nonionic surfactant as a surfactant.

作為陰離子性界面活性劑，例如可舉出烷基苯磺酸鹽、烷基硫酸酯鹽、聚氧乙烯烷基醚硫酸酯鹽、脂肪酸鹽等。　　作為非離子性界面活性劑，例如可舉出聚乙烯醇、聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚、聚氧乙烯多環苯基醚、聚氧化烯烷基醚、山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇酐脂肪酸酯等。　　作為陽離子性界面活性劑，例如可舉出鯨蠟基三甲基銨溴化物、月桂基吡啶鎓氯化物等。As anionic surfactant, alkylbenzenesulfonate, alkylsulfate, polyoxyethylene alkyl ether sulfate, fatty acid salt, etc. are mentioned, for example. Examples of nonionic surfactants include polyvinyl alcohol, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxyalkylene alkyl ether, and sorbose. Alcohol anhydride fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Examples of the cationic surfactant include cetyltrimethylammonium bromide, laurylpyridinium chloride, and the like.

作為共聚合性界面活性劑，可使用在分子內具有至少1個以上的能自由基聚合之不飽和雙鍵性基的陰離子性或非離子性界面活性劑。作為共聚合性界面活性劑，例如可舉出具有硫酸銨鹽基(-SO^3- NH⁴⁺ )等的硫酸鹽基與烯丙基(-CH₂ -CH=CH₂ )之烴化合物、具有硫酸銨鹽基 (-SO^3- NH⁴⁺ )等的硫酸鹽基與甲基丙烯醯基[-CO-C(CH₃ )=CH₂ ]之烴化合物、或具有硫酸銨鹽基(-SO^3- NH⁴⁺ )等的硫酸鹽基與1-丙烯基(-CH=CH₂ CH₃ )之芳香族烴化合物等。As the copolymerizable surfactant, an anionic or nonionic surfactant having at least one radically polymerizable unsaturated double bond group in the molecule can be used. Examples of the copolymerizable surfactant include hydrocarbon compounds having a sulfate group such as an ammonium sulfate group (-SO ^3- NH ⁴⁺ ) and an allyl group (-CH ₂ -CH=CH ₂ ), Hydrocarbon compounds of sulfate groups such as ammonium sulfate groups (-SO ^3- NH ⁴⁺ ) and methacryloyl groups [-CO-C(CH ₃ )=CH ₂ ], or ammonium sulfate groups (-SO ^3- NH ⁴⁺ ) and other sulfate groups and 1-propenyl (-CH=CH ₂ CH ₃ ) aromatic hydrocarbon compounds and the like.

界面活性劑之使用量係可任意地選擇，但為了保持乳化的安定性，相對於原料的含磷不飽和單體(A)與聚合性不飽和單體(B)之合計100質量份，較佳為0.01～40質量份，更佳為0.05～20質量份，尤佳為0.1～10質量份。The amount of surfactant used can be arbitrarily selected, but in order to maintain the stability of the emulsification, it is more 0.01-40 mass parts is preferable, 0.05-20 mass parts is more preferable, 0.1-10 mass parts is especially preferable.

＜中和劑＞　　中和劑係在製造包含共聚物的樹脂組成物時視需要而使用。藉由使用中和劑來調整包含共聚物的樹脂組成物之pH，可得到樹脂組成物中的混和安定性升高，或可抑制滲出之效果。　　作為中和劑，可使用習知的化合物。例如，可使用氫氧化鈉水溶液、氨水溶液、單甲基胺等之單烷基胺等。<Neutralizer> Neutralizers are used as necessary when producing a resin composition containing a copolymer. By adjusting the pH of the resin composition containing the copolymer using a neutralizing agent, the mixing stability in the resin composition can be improved, or the effect of suppressing bleeding can be obtained. As the neutralizing agent, a known compound can be used. For example, an aqueous sodium hydroxide solution, an aqueous ammonia solution, a monoalkylamine such as monomethylamine, and the like can be used.

＜水溶性高分子＞　　水溶性高分子係在製造共聚物時視需要而使用。水溶性高分子係將共聚物予以保護膠體化，使其安定地分散於水性溶劑中者。作為水溶性高分子，可使用水溶性(甲基)丙烯酸樹脂、水溶性(甲基)丙烯酸酯樹脂、聚氧乙烯烷基醚等。此等之水溶性高分子係可無關於皂化度、平均聚合度、有無改性而使用。從製造共聚物時的聚合安定性及共聚物的黏度之觀點來看，水溶性高分子之平均聚合度較佳為200～2,400。從製造共聚物時的聚合安定性之觀點來看，水溶性高分子之皂化度較佳為80%～100%。　　還有，於水溶性高分子亦為聚合性不飽和單體(B)時，視為聚合性不飽和單體(B)。<Water-soluble polymer> The water-soluble polymer is used as necessary when producing a copolymer. The water-soluble polymer is a protective colloid of the copolymer, which is stably dispersed in an aqueous solvent. As a water-soluble polymer, a water-soluble (meth)acrylic resin, a water-soluble (meth)acrylate resin, a polyoxyethylene alkyl ether, etc. can be used. These water-soluble polymers can be used regardless of the degree of saponification, the average degree of polymerization, and the presence or absence of modification. The average degree of polymerization of the water-soluble polymer is preferably 200 to 2,400 from the viewpoints of the polymerization stability and the viscosity of the copolymer when the copolymer is produced. The degree of saponification of the water-soluble polymer is preferably from 80% to 100%, from the viewpoint of the polymerization stability during the production of the copolymer. In addition, when the water-soluble polymer is also the polymerizable unsaturated monomer (B), it is regarded as the polymerizable unsaturated monomer (B).

使用水溶性高分子時的使用量係可任意地選擇，但為了保持分散安定性，相對於原料的含磷不飽和單體(A)與聚合性不飽和單體(B)之合計100質量份，較佳為0.01～40質量份，更佳為0.05～20質量份，尤佳為0.1～10質量份。The amount used when using the water-soluble polymer can be arbitrarily selected, but in order to maintain dispersion stability, it is based on 100 parts by mass of the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) of the raw material , preferably 0.01 to 40 parts by mass, more preferably 0.05 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass.

本實施形態之共聚物包含來自含磷不飽和單體(A)的構成成分與來自聚合性不飽和單體(B)的構成成分，來自(B)的構成成分包含來自具有碳原子數及氧原子數之合計為4～10的主鏈之不飽和羧酸單體(b-1)的構成成分，且相對於來自(A)的構成成分與來自(B)的構成成分之合計含量，來自具有碳數為1～4的烷基之(甲基)丙烯酸烷酯單體(b-2)的構成成分之含量為0.00～1.00質量%，難燃性優異。　　本實施形態之共聚物的難燃性，推測係藉由來自(A)的構成成分與不飽和羧酸單體(b-1)的構成成分中所包含的羧基之相乘效果，促進燃燒時的碳化層形成藉此可得者。The copolymer of the present embodiment includes a component derived from the phosphorus-containing unsaturated monomer (A) and a component derived from a polymerizable unsaturated monomer (B), and the component derived from (B) includes a component derived from the unsaturated monomer having the number of carbon atoms and oxygen Constituents of the main chain unsaturated carboxylic acid monomer (b-1) whose total number of atoms is 4 to 10, and the total content of the constituents derived from (A) and the constituents derived from (B) is derived from The content of the constituent components of the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms is 0.00 to 1.00 mass %, and it is excellent in flame retardancy. The flame retardancy of the copolymer of the present embodiment is presumed to be due to the synergistic effect of the component derived from (A) and the carboxyl group contained in the component of the unsaturated carboxylic acid monomer (b-1), when combustion is accelerated. The carbide layer formed by this can be obtained.

本實施形態之共聚物具有優異的難燃化性能。因此，於包含本實施形態的共聚物作為難燃劑的加工品中，可使難燃劑之含量成為比較少量。因此，於包含本實施形態之共聚物作為難燃劑的加工品中，難燃劑賦予加工品之物性之影響較少。　　又，由於本實施形態之共聚物同時包含來自(A)的構成成分與來自(B)的構成成分，使用作為加工品的材料時，得到抗滲出性及抗黏連性良好之加工品。The copolymer of this embodiment has excellent flame retardancy. Therefore, in the processed product containing the copolymer of this embodiment as a flame retardant, the content of the flame retardant can be made to be relatively small. Therefore, in the processed product containing the copolymer of this embodiment as a flame retardant, the effect of the flame retardant on the physical properties of the processed product is small. Furthermore, since the copolymer of the present embodiment contains both the constituents derived from (A) and the constituents derived from (B), when used as a material for a processed product, a processed product with good bleed resistance and blocking resistance can be obtained.

[樹脂組成物] 　　本實施形態之樹脂組成物包含上述實施形態之共聚物。本實施形態之樹脂組成物只要是包含上述實施形態之共聚物者即可，例如除了上述實施形態之共聚物之外，還可包含上述的溶劑、界面活性劑、起始劑、中和劑等。本實施形態之樹脂組成物係可為在製造上述實施形態之共聚物的過程中所得者。前述樹脂組成物係可以任意之量包含上述共聚物，但若舉例，則前述組成物中的前述共聚物之量較佳為1.0～90質量%，更佳為10～85質量%，尤佳為15～80質量%。惟，不限定於此等範圍。例如，亦可為0.1～1.0質量%，或90～95質量%。[Resin composition] The resin composition of the present embodiment includes the copolymer of the above-described embodiment. The resin composition of the present embodiment only needs to contain the copolymer of the above-mentioned embodiment, and for example, in addition to the copolymer of the above-mentioned embodiment, the above-mentioned solvent, surfactant, initiator, neutralizer, etc. may be contained. . The resin composition of this embodiment can be obtained in the process of manufacturing the copolymer of the said embodiment. The resin composition may contain the above-mentioned copolymer in any amount, but as an example, the amount of the above-mentioned copolymer in the composition is preferably 1.0 to 90% by mass, more preferably 10 to 85% by mass, particularly preferably 15 to 80 mass %. However, it is not limited to these ranges. For example, it may be 0.1 to 1.0 mass %, or 90 to 95 mass %.

[處理劑] 　　本實施形態之處理劑包含上述實施形態之共聚物。作為本實施形態之處理劑，例如可舉出使共聚物分散或溶解於上述溶劑中者。如此的處理劑係藉由塗佈於基材而附著於基材上，藉由去除溶劑而形成包含共聚物的塗膜。因此，本實施形態之處理劑係可使用作為塗料、紙處理劑、纖維處理劑、接著劑、黏著劑等。　　作為本實施形態之處理劑，可直接使用將上述製造方法所製造的共聚物分散或溶解在溶劑中之樹脂組成物。[Treatment agent] The treatment agent of this embodiment contains the copolymer of the above-mentioned embodiment. As a processing agent of this embodiment, the thing which disperse|distributed or melt|dissolved a copolymer in the said solvent is mentioned, for example. Such a treatment agent is applied to a substrate to adhere to a substrate, and a coating film containing a copolymer is formed by removing the solvent. Therefore, the treatment agent of this embodiment can be used as a paint, a paper treatment agent, a fiber treatment agent, an adhesive, an adhesive, and the like. As the treatment agent of the present embodiment, a resin composition obtained by dispersing or dissolving the copolymer produced by the above-mentioned production method in a solvent can be used as it is.

本說明書中之所謂「處理劑」，就是定義為除了紙處理劑、纖維處理劑等之外，還包含塗料及黏接著劑者。　　所謂處理劑的「固體成分」，就是定義為使處理劑中所包含的溶劑乾燥者。The so-called "treatment agent" in this specification is defined to include a paint and an adhesive in addition to a paper treatment agent, a fiber treatment agent, and the like. The "solid content" of the treatment agent is defined as drying the solvent contained in the treatment agent.

＜其他樹脂＞　　於不損害本發明效果之範圍內，本實施形態之處理劑係可按照用途，含有與上述實施形態之共聚物不同的其他樹脂。　　作為其他樹脂，可舉出丙烯酸樹脂、環氧樹脂、胺基甲酸酯樹脂、聚酯樹脂等之各種樹脂。其他樹脂亦可為樹脂乳液或溶液樹脂之狀態。本實施形態之處理劑中的上述實施形態之共聚物與其他各種樹脂之混合比例係可任意。<Other resins> The treatment agent of the present embodiment may contain other resins different from the copolymer of the above-mentioned embodiment in accordance with the application within the range that does not impair the effect of the present invention. As other resins, various resins such as acrylic resins, epoxy resins, urethane resins, and polyester resins can be mentioned. Other resins can also be in the state of resin emulsion or solution resin. The mixing ratio of the copolymer of the above-mentioned embodiment and other various resins in the treatment agent of the present embodiment is arbitrary.

＜其他成分＞　　本實施形態之處理劑係除了共聚物之外，視需要還可含有其他成分。　　作為其他成分，例如可按照用途，於不損害本發明目的之範圍內，方便地選擇交聯劑、增黏劑、酸或鹼等之pH調整劑、成膜助劑、可塑劑、防腐劑、消泡劑、顏料、分散劑、光安定劑、紫外線吸收劑、抗氧化劑、防鏽劑、浸透劑、抗靜電劑、調平劑、增黏劑等眾所周知慣用添加劑而含有。<Other components> The treatment agent of the present embodiment may contain other components as necessary in addition to the copolymer. As other components, for example, cross-linking agents, tackifiers, pH adjusters such as acids or bases, film-forming aids, plasticizers, preservatives, Defoamers, pigments, dispersants, light stabilizers, ultraviolet absorbers, antioxidants, rust inhibitors, penetrants, antistatic agents, levelers, tackifiers and other well-known conventional additives are contained.

本實施形態之處理劑例如係可藉由使用以往習知的方法，混合上述實施形態的共聚物、上述溶劑、視需要使用的其他樹脂與其他成分中的至少1者之方法而製造。在製造處理劑時，例如可使用各種磨機、溶解器等之混合裝置進行混合。The processing agent of this embodiment can be manufactured by the method of mixing at least one of the copolymer of the said embodiment, the said solvent, other resin used as needed, and other components, for example using a conventionally known method. When producing the treatment agent, for example, mixing can be performed using various mixing devices such as a mill and a dissolver.

本實施形態之處理劑由於包含本實施形態之共聚物，可得到難燃性優異，抗滲出性及抗黏連性良好之塗膜。　　本實施形態之處理劑由於可賦予基材優異的難燃性，可適用於各種領域。Since the treating agent of the present embodiment contains the copolymer of the present embodiment, a coating film having excellent flame retardancy and good bleed resistance and blocking resistance can be obtained. Since the treatment agent of this embodiment can impart excellent flame retardancy to the base material, it can be applied to various fields.

[加工品] 　　本實施形態之加工品具有基材與附著於前述基材上的上述實施形態之共聚物、樹脂組成物或處理劑。　　作為本實施形態之加工品，例如可舉出紙加工品、纖維加工品、一般加工品、接著劑加工品、黏著劑加工品等。[Processed Product] The processed product of this embodiment has a base material and the copolymer, resin composition or treatment agent of the above-mentioned embodiment adhered to the base material. As the processed product of the present embodiment, for example, a paper processed product, a fiber processed product, a general processed product, an adhesive processed product, an adhesive processed product, and the like can be mentioned.

於本實施形態之加工品中，相對於加工品，附著於基材上的處理劑之固體成分較佳為5～70質量%，更佳為10～60質量%，尤佳為20～50質量%。若處理劑之固體成分的附著量為5質量%以上，則可容易得到難燃性良好的加工品。若處理劑之固體成分的附著量為70質量%以下，則可抑制因處理劑中的共聚物附著於基材之表面所致的外觀不良。In the processed product of the present embodiment, the solid content of the treatment agent adhering to the substrate is preferably 5 to 70 mass %, more preferably 10 to 60 mass %, and particularly preferably 20 to 50 mass % with respect to the processed product %. When the adhesion amount of the solid content of the treatment agent is 5 mass % or more, a processed product with good flame retardancy can be easily obtained. If the adhesion amount of the solid content of the treatment agent is 70% by mass or less, it is possible to suppress poor appearance due to the adhesion of the copolymer in the treatment agent to the surface of the base material.

本實施形態之加工品係相對於基材100質量份，共聚物之含量較佳為1～70質量份。共聚物之含量之下限值更佳為20質量份以上，尤佳為40質量份以上。共聚物之含量之上限值更佳為65質量份以下，尤佳為60質量份以下。若共聚物之含量為1質量份以上，則更有效果地得到包含共聚物所致的難燃性提高效果。若共聚物之含量為70質量份以下，則變可容易得到按照用途的加工品。In the processed product of the present embodiment, the content of the copolymer is preferably 1 to 70 parts by mass relative to 100 parts by mass of the base material. The lower limit value of the content of the copolymer is more preferably 20 parts by mass or more, particularly preferably 40 parts by mass or more. The upper limit value of the content of the copolymer is more preferably 65 parts by mass or less, particularly preferably 60 parts by mass or less. When the content of the copolymer is 1 part by mass or more, the effect of improving the flame retardancy by including the copolymer is more effectively obtained. When the content of the copolymer is 70 parts by mass or less, it becomes easy to obtain a processed product according to the application.

本實施形態之加工品例如係可藉由將本實施形態之處理劑塗佈或含浸，使其乾燥，使共聚物附著於基材之方法而製造。The processed product of the present embodiment can be produced by, for example, applying or impregnating the treating agent of the present embodiment, drying it, and attaching the copolymer to a substrate.

本實施形態之加工品具有基材與附著於前述基材上的本實施形態之共聚物。因此，本實施形態之加工品具有優異的難燃性、抗滲出性及抗黏連性。因此，本實施形態之加工品係可適用於各種領域。The processed product of this embodiment has a base material and the copolymer of this embodiment attached to the said base material. Therefore, the processed product of this embodiment has excellent flame retardancy, bleed resistance and blocking resistance. Therefore, the processed strain of this embodiment can be applied to various fields.

「具體例」　　接著，作為本實施形態之處理劑及加工品的具體例，分別說明「紙處理劑及紙加工品」、「纖維處理劑及纖維加工品」、「一般塗料及一般加工品」、「黏接著劑及黏接著劑加工品」。　　還有，在本說明書中所謂「黏接著劑」，就是意指具有黏著劑與接著劑之任一者或兩者的機能之處理劑。"Specific examples" Next, as specific examples of the processing agent and processed product of the present embodiment, "paper processing agent and paper processed product", "fiber processing agent and fiber processed product", and "general paint and general processed product" will be described, respectively. , "Adhesives and Adhesives Processed Products". In addition, the term "adhesive agent" in this specification means a treatment agent having the functions of either or both of an adhesive agent and an adhesive agent.

「紙處理劑及紙加工品」 (紙處理劑) 　　作為本實施形態之紙處理劑，可使用使任意地選擇之量的本實施形態之共聚物溶解或分散於溶劑者。　　於本實施形態中，紙處理劑中的共聚物之含量較佳為1～90質量%，更佳為10～80質量%。藉由成為共聚物之含量為上述範圍的紙處理劑，包含共聚物所致的效果變更顯著。"Paper processing agent and paper processed product" (paper processing agent) As the paper processing agent of the present embodiment, one in which an arbitrarily selected amount of the copolymer of the present embodiment is dissolved or dispersed in a solvent can be used. In the present embodiment, the content of the copolymer in the paper treating agent is preferably 1 to 90% by mass, more preferably 10 to 80% by mass. By making it into the paper processing agent whose content of a copolymer is the said range, the effect by containing a copolymer changes remarkably.

(紙加工品) 　　於本實施形態之紙加工品中，使用紙作為基材。作為紙，例如可舉出由紙漿纖維素所構成之通用的紙類等。(Paper processed product) In the paper processed product of the present embodiment, paper is used as a base material. As paper, general-purpose paper etc. which consist of pulp cellulose are mentioned, for example.

紙處理劑對於紙加工品之使用量(附著量)，係可按照所用的基材本身之難燃性等而適宜變更。紙處理劑之乾燥後的附著量(固體成分)係可任意地選擇，但相對於紙加工品，較佳為5～70質量%，更佳為10～60質量%，尤佳為20～50質量%。若紙處理劑之附著量為5質量%以上，則可容易得到難燃性良好的紙加工品。若紙處理劑之附著量為70質量%以下，則可抑制因在由紙所構成的基材之表面附著紙處理劑中的共聚物所造成的強度及手感之降低。The usage-amount (adhesion amount) of a paper treating agent to a paper-processed product can be suitably changed according to the flame retardance of the base material itself used, etc.. The adhesion amount (solid content) after drying of the paper treatment agent can be arbitrarily selected, but is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and particularly preferably 20 to 50% by mass relative to the processed paper product. quality%. When the adhesion amount of the paper processing agent is 5 mass % or more, a paper processed product with good flame retardancy can be easily obtained. When the adhesion amount of the paper treatment agent is 70 mass % or less, the decrease in strength and texture due to the adhesion of the copolymer in the paper treatment agent to the surface of the substrate made of paper can be suppressed.

紙加工品中的共聚物之附著量(含量)係可任意地選擇，但相對於紙(基材)100質量份，較佳為1～70質量份，更佳為3～60質量份，尤佳為5～50質量份。若共聚物之附著量為1質量份以上，則可容易得到難燃性良好的紙加工品。若共聚物之附著量為70質量份以下，則可抑制因在由紙所構成的基材之表面附著共聚物而造成的強度及手感之降低。The adhesion amount (content) of the copolymer in the paper processed product can be arbitrarily selected, but is preferably 1 to 70 parts by mass, more preferably 3 to 60 parts by mass, relative to 100 parts by mass of the paper (substrate), especially Preferably it is 5-50 mass parts. When the adhesion amount of the copolymer is 1 part by mass or more, it is easy to obtain a paper processed product with good flame retardancy. If the adhesion amount of the copolymer is 70 parts by mass or less, the decrease in strength and texture due to the adhesion of the copolymer to the surface of the substrate made of paper can be suppressed.

(紙加工品之製造方法) 　　作為本實施形態的紙加工品之製造方法，可無特別限制地採用以往習知的方法。例如，可舉出於由紙所構成的基材，塗佈或含浸本實施形態的紙處理劑後，使其乾燥之方法。　　作為於由紙所構成的基材塗佈紙處理劑之方法，可使用以往習知的方法。例如，可舉出於紙處理劑中浸漬基材之方法(浸漬)、噴霧塗佈、輥塗佈等。藉由此等之塗佈方法，於基材塗佈紙處理劑後，使用軋液輥等，壓榨塗佈有紙處理劑的基材，藉此亦可調整附著或含浸於基材的紙處理劑之附著量。(Manufacturing method of paper processed product) As the manufacturing method of the paper processed product of the present embodiment, a conventionally known method can be adopted without particular limitation. For example, after applying or impregnating the paper treating agent of the present embodiment to a substrate made of paper, and drying the substrate can be mentioned. As a method of applying a paper treating agent to a substrate made of paper, a conventionally known method can be used. For example, the method of impregnating the substrate in the paper treatment agent (dipping), spray coating, roll coating, and the like are exemplified. By such a coating method, after the paper treatment agent is applied to the substrate, the substrate coated with the paper treatment agent is squeezed using a nip roll or the like, thereby adjusting the paper treatment that adheres to or impregnates the substrate. Adhesion amount of the agent.

作為使塗佈有紙處理劑的基材乾燥之方法，可使用以往習知的方法。例如，可對於塗佈有紙處理劑的基材，進行送風乾燥，也可減壓乾燥，亦可加壓乾燥。　　使塗佈有紙處理劑的基材乾燥時，亦可將塗佈有紙處理劑的基材加熱。將塗佈有紙處理劑的基材加熱而使其乾燥時的加熱溫度係可任意地選擇，但較佳為50～250℃，更佳為80～190℃，尤佳為90～150℃。若上述加熱溫度為50℃以上，則因加熱而促進塗佈有紙處理劑的基材之乾燥。若上述加熱溫度為250℃以下，則可抑制因加熱而塗佈有紙處理劑的基材變質。As a method of drying the substrate coated with the paper treatment agent, a conventionally known method can be used. For example, the base material coated with the paper treatment agent may be air-dried, may be dried under reduced pressure, or may be dried under pressure. When drying the substrate coated with the paper treatment agent, the substrate coated with the paper treatment agent can also be heated. The heating temperature at the time of heating and drying the substrate coated with the paper treatment agent can be arbitrarily selected, but is preferably 50 to 250°C, more preferably 80 to 190°C, particularly preferably 90 to 150°C. When the said heating temperature is 50 degreeC or more, drying of the base material which apply|coated the paper processing agent will be accelerated|stimulated by heating. If the said heating temperature is 250 degrees C or less, it can suppress that the base material to which the paper processing agent was apply|coated by heating is changed in quality.

本實施形態之加工品的紙加工品具有優異的難燃性、抗滲出性及抗黏連性。又，本實施形態之紙加工品係因為在由紙所構成的基材上附著有共聚物，而具有優異的強度。基於此等，本實施形態之紙加工品例如係可適合作為壁紙、壁紙用襯底紙等之建築材料、家電、電子材料、汽車內部裝飾材料用途之材料。The paper processed product of the processed product of the present embodiment has excellent flame retardancy, bleed resistance and blocking resistance. In addition, the paper-processing product of the present embodiment has excellent strength because the copolymer is attached to the substrate made of paper. Based on these, the paper-processed product of this embodiment is suitable for use as building materials such as wallpaper and backing paper for wallpaper, home appliances, electronic materials, and automotive interior materials, for example.

「纖維處理劑及纖維加工品」 (纖維處理劑) 　　作為本實施形態之纖維處理劑，可使用使本實施形態之共聚物溶解或分散於溶劑中者。　　於本實施形態中，纖維處理劑中的共聚物之含量係可任意地選擇，但較佳為1～90質量%，更佳為10～80質量%。藉由成為共聚物之含量為上述範圍之纖維處理劑，包含共聚物所致的效果變更顯著。"Fiber-treating agent and fiber-processed product" (fiber-treating agent) As the fiber-treating agent of the present embodiment, one obtained by dissolving or dispersing the copolymer of the present embodiment in a solvent can be used. In the present embodiment, the content of the copolymer in the fiber treatment agent can be arbitrarily selected, but is preferably 1 to 90% by mass, more preferably 10 to 80% by mass. By making it into the fiber treatment agent whose content of a copolymer is the said range, the effect by containing a copolymer changes remarkably.

(纖維加工品) 　　於本實施形態之纖維加工品中，使用纖維作為基材。　　纖維之形狀係沒有特別的限定，例如可將不織布、織物、針織物、形成薄片狀的纖維予以毛網化而成為毛網(web)，接著或纏結所得之毛網而布形化者等。(Fiber Processed Product) In the fiber processed product of the present embodiment, fiber is used as a base material. The shape of the fibers is not particularly limited. For example, nonwoven fabrics, woven fabrics, knitted fabrics, and flake-shaped fibers can be made into a fleece to form a web, and then the obtained fleece can be entangled to form a fabric, etc. .

纖維之材料係沒有特別的限定，例如可舉出棉花、麻、蠶絲、羊毛、膠原纖維、丙烯酸纖維、纖維素系纖維、聚醯亞胺纖維、聚醯胺醯亞胺纖維、縲縈纖維、尼龍纖維、維尼綸纖維、聚酯纖維、聚丙烯纖維、聚氯乙烯纖維、聚乙烯纖維、聚間伸苯基間苯二甲醯胺纖維、芳香族聚醯胺纖維、聚芳酯纖維、聚四氟乙烯纖維、聚苯并咪唑纖維、聚醚醚酮纖維、聚苯硫纖維及此等之混紡品等。The material of the fiber is not particularly limited, for example, cotton, hemp, silk, wool, collagen fibers, acrylic fibers, cellulose fibers, polyimide fibers, polyimide fibers, rayon fibers, Nylon fiber, vinylon fiber, polyester fiber, polypropylene fiber, polyvinyl chloride fiber, polyethylene fiber, polym-phenylene isophthalamide fiber, aromatic polyamide fiber, polyarylate fiber, poly Tetrafluoroethylene fiber, polybenzimidazole fiber, polyether ether ketone fiber, polyphenylene sulfide fiber and their blends, etc.

纖維處理劑對於纖維加工品之使用量(附著量)，係可按照所用的基材本身之難燃性等而適宜變更。相對於纖維加工品，纖維處理劑之乾燥後的附著量(固體成分)較佳為5～70質量%，更佳為10～60質量%，尤佳為20～50質量%。若纖維處理劑之附著量為5質量%以上，則可容易得到難燃性良好的纖維加工品。若纖維處理劑之附著量為70質量%以下，則可抑制因在由纖維所構成的基材之表面附著纖維處理劑中的共聚物所造成的強度及手感之降低。The usage amount (adhesion amount) of the fiber treatment agent to the fiber processed product can be appropriately changed according to the flame retardancy of the base material itself to be used. The adhesion amount (solid content) of the fiber treatment agent after drying is preferably 5 to 70 mass %, more preferably 10 to 60 mass %, and particularly preferably 20 to 50 mass % with respect to the fiber processed product. When the adhesion amount of the fiber treatment agent is 5 mass % or more, a fiber processed product with good flame retardancy can be easily obtained. If the adhesion amount of the fiber treatment agent is 70 mass % or less, the decrease in strength and texture due to adhesion of the copolymer in the fiber treatment agent to the surface of the base material composed of fibers can be suppressed.

纖維加工品中的共聚物之附著量(含量)係可任意地選擇，但相對於纖維(基材)100質量份，較佳為1～70質量份，更佳為3～60質量份，尤佳為5～50質量份。若共聚物之附著量為1質量份以上，則可容易得到難燃性良好的纖維加工品。若共聚物之附著量為70質量份以下，則可抑制因在由纖維所構成的基材之表面附著共聚物所造成的強度及手感之降低。The adhesion amount (content) of the copolymer in the fiber processed product can be arbitrarily selected, but is preferably 1 to 70 parts by mass, more preferably 3 to 60 parts by mass, relative to 100 parts by mass of the fiber (substrate), especially Preferably it is 5-50 mass parts. When the adhesion amount of the copolymer is 1 part by mass or more, a fiber processed product with good flame retardancy can be easily obtained. If the adhesion amount of the copolymer is 70 parts by mass or less, the decrease in strength and texture due to the adhesion of the copolymer to the surface of the base material composed of fibers can be suppressed.

(纖維加工品之製造方法) 　　作為本實施形態的纖維加工品之製造方法，可無特別限制地採用以往習知的方法。例如，可舉出於由纖維所構成的基材，塗佈或含浸本實施形態的纖維處理劑後，使其乾燥之方法。　　作為於由纖維所構成的基材塗佈紙處理劑之方法，可使用以往習知的方法。例如，可舉出於纖維處理劑中浸漬基材之方法(浸漬)、直接塗佈法、噴霧塗佈法、輥塗法、槽塗法、刮刀塗佈法、印刷法、輥轉印法、背面塗佈法等。作為於纖維處理劑中浸漬基材之方法，可舉出水平輥法、金屬輥法、網輸送法、發泡法等。(Manufacturing method of fiber processed product) As the manufacturing method of the fiber processed product of the present embodiment, a conventionally known method can be adopted without particular limitation. For example, after applying or impregnating the fiber treatment agent of the present embodiment to a base material made of fibers, a method of drying it can be mentioned. As a method of applying a paper treatment agent to a substrate made of fibers, a conventionally known method can be used. For example, a method of dipping a substrate into a fiber treatment agent (dipping), a direct coating method, a spray coating method, a roll coating method, a slot coating method, a blade coating method, a printing method, a roll transfer method, Back coating method, etc. As a method of impregnating the base material in the fiber treatment agent, a horizontal roll method, a metal roll method, a web conveying method, a foaming method, etc. are mentioned.

當纖維的形狀為不織布時，作為在纖維上塗佈纖維處理劑之方法，較佳為使用噴霧塗佈法、印刷法、輥轉印法、水平輥法、金屬輥法、網輸送法、發泡法等。　　當纖維的形狀為織物時，作為在纖維上塗佈纖維處理劑之方法，較佳為使用直接塗佈法、噴霧塗佈法、輥塗法、槽塗法、刮刀塗佈法等。When the shape of the fibers is non-woven, as a method for coating the fibers with the fiber treatment agent, spray coating, printing, roll transfer, horizontal roll, metal roll, web conveying, hair bubble method, etc. When the shape of the fiber is a fabric, as a method for coating the fiber with the fiber treatment agent, it is preferable to use a direct coating method, a spray coating method, a roll coating method, a slot coating method, a blade coating method, or the like.

作為基材，使用將形成薄片狀的纖維予以毛網化而成為毛網，接著或纏結所得之毛網而布形化者時，纖維處理劑對基材之塗佈係可對於毛網化之前的纖維進行，也可將纖維毛網化後而進行。　　作為將纖維予以毛網化之方法，可無特別限制地使用各種眾所周知的方法，例如可舉出氣流成網法等。As the base material, when the fibers formed into flakes are made into a fleece, and then the fleece obtained by entanglement is used to form a fleece, the coating of the fiber treatment agent on the base material can be used for the fleece formation. It can also be carried out after the previous fiber is made into a netting. As a method of making fibers into a fleece, various well-known methods can be used without particular limitation, for example, an air-laid method and the like can be mentioned.

作為使塗佈有纖維處理劑的基材乾燥之方法，可使用以往習知的方法。例如，可對於塗佈有纖維處理劑的基材，進行送風乾燥，也可減壓乾燥，亦可加壓乾燥。　　使塗佈有纖維處理劑的基材乾燥時，亦可將塗佈有纖維處理劑的基材加熱。將塗佈有纖維處理劑的基材加熱而使其乾燥時的加熱溫度係可任意地選擇，但較佳為50～250℃，更佳為80～190℃。若上述加熱溫度為50℃以上，則因加熱而促進塗佈有纖維處理劑的基材之乾燥。若上述加熱溫度為250℃以下，則可抑制因加熱而塗佈有纖維處理劑的基材變質。A conventionally known method can be used as a method of drying the base material coated with the fiber treatment agent. For example, the base material coated with the fiber treatment agent may be air-dried, may be dried under reduced pressure, or may be dried under pressure. When drying the substrate coated with the fiber treatment agent, the substrate coated with the fiber treatment agent can also be heated. The heating temperature at the time of heating and drying the base material coated with the fiber treatment agent can be arbitrarily selected, but is preferably 50 to 250°C, more preferably 80 to 190°C. When the said heating temperature is 50 degreeC or more, drying of the base material which apply|coated the fiber treatment agent by heating will be accelerated|stimulated. If the said heating temperature is 250 degrees C or less, it can suppress that the base material to which the fiber processing agent was apply|coated by heating is changed in quality.

本實施形態之加工品的纖維加工品具有優異的難燃性、抗滲出性及抗黏連性。又，本實施形態之纖維加工品係因為在由纖維所構成的基材上附著有共聚物，而具有優異的強度。基於此等，本實施形態之纖維加工品例如係可適合作為窗簾等的內部裝飾材料、家電用緩衝材等的家電、電子材料用緩衝材等的電子材料、汽車內裝緩衝材及汽車椅墊等的汽車內部裝飾材料用途之材料。The fiber processed product of the processed product of the present embodiment has excellent flame retardancy, bleed resistance and blocking resistance. In addition, the fiber-processed product of the present embodiment has excellent strength because the copolymer is attached to the base material made of fibers. Based on this, the fiber processed product of the present embodiment can be suitably used as, for example, interior materials such as curtains, home appliances such as home appliance cushioning materials, electronic materials such as cushioning materials for electronic materials, automobile interior cushioning materials, and automobile seat cushions. Materials used for automotive interior decoration materials, etc.

「一般塗料及一般加工品」 (一般塗料) 　　本實施形態之一般塗料係塗佈於基材者，使用本實施形態之處理劑。　　於本實施形態中，一般塗料中的共聚物之含量係可任意地選擇，但較佳為1～90質量%，更佳為10～80質量%。藉由成為共聚物之含量為上述範圍的一般塗料，包含共聚物所致的效果變更顯著。"General paint and general processed products" (general paint) The general paint of this embodiment is applied to a substrate, and the treatment agent of this embodiment is used. In this embodiment, the content of the copolymer in the general coating material can be arbitrarily selected, but is preferably 1 to 90% by mass, more preferably 10 to 80% by mass. By making it into a general coating material whose content of a copolymer is the said range, the effect by containing a copolymer changes remarkably.

(一般加工品) 　　本實施形態之一般加工品係在基材塗佈一般塗料而形成者。作為一般加工品中使用的基材之材料，例如可舉出玻璃、聚烯烴樹脂、聚酯樹脂、聚碳酸酯樹脂、丙烯腈丁二烯苯乙烯共聚物(ABS樹脂)、聚苯乙烯樹脂等之樹脂、金屬、木材、紙等，不受此等所限定。　　一般加工品中使用的基材之形狀係沒有特別的限定，例如可成為薄膜、薄片、杯等之形狀。(General processed product) The general processed product of the present embodiment is formed by coating a general coating on a substrate. Examples of the material of the base material used in general processed products include glass, polyolefin resin, polyester resin, polycarbonate resin, acrylonitrile butadiene styrene copolymer (ABS resin), polystyrene resin, and the like. Resin, metal, wood, paper, etc., are not limited by these. The shape of the substrate used in general processed products is not particularly limited, for example, it can be in the shape of a film, a sheet, a cup, etc.

一般塗料對於一般加工品之使用量(附著量)，係可按照所用的基材本身之難燃性等而適宜變更。一般塗料的乾燥後之附著量(固體成分)係可任意地選擇，但相對於一般加工品，較佳為5～70質量%，更佳為10～60質量%，尤佳為20～50質量%。若一般塗料之附著量為5質量%以上，則可容易得到難燃性良好的一般加工品。若一般塗料之附著量為70質量%以下，則可抑制因在基材之表面上附著一般塗料中的共聚物所造成的外觀不良。The usage amount (adhesion amount) of general coatings to general processed products can be appropriately changed according to the flame retardancy of the substrate itself to be used. The adhesion amount (solid content) after drying of a general paint can be arbitrarily selected, but is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and particularly preferably 20 to 50% by mass relative to a general processed product %. When the adhesion amount of a general paint is 5 mass % or more, a general processed product with good flame retardancy can be easily obtained. When the adhesion amount of a general paint is 70 mass % or less, it can suppress the appearance defect by the copolymer in a general paint adhering to the surface of a base material.

(一般加工品之製造方法) 　　作為本實施形態的一般加工品之製造方法，可無特別限制地採用以往習知的方法。例如，可舉出於由樹脂、金屬等所構成的基材，塗佈本實施形態之一般塗料後，使其乾燥之方法。　　作為一般加工品中使用的基材上塗佈一般塗料之方法，可使用以往習知的方法。例如，可舉出於一般塗料中浸漬基材之方法(浸漬)，使用噴霧、刷毛塗佈、輥塗、鏝刀塗佈、氣刀、流塗、棒塗、輥塗、凹版塗佈、塗抹器等之方法。(Manufacturing method of general processed product) As the manufacturing method of the general processed product of the present embodiment, a conventionally known method can be adopted without particular limitation. For example, after applying the general coating material of this embodiment to a base material made of resin, metal, or the like, a method of drying it can be mentioned. As a method of applying a general paint to a substrate used in general processed products, a conventionally known method can be used. For example, as a method of dipping a substrate in a general coating material (dipping), spray coating, brush coating, roll coating, trowel coating, air knife coating, flow coating, bar coating, roll coating, gravure coating, painting method, etc.

於基材塗佈一般塗料時的膜厚係沒有特別的限定，可任意地選擇。例如，較佳為1～200μm，更佳為10～150μm，尤佳為10～100μm。若塗佈一般塗料的膜厚為1μm以上，則可容易得到難燃性良好的一般加工品。若塗佈一般塗料的膜厚為200μm以下，則抑制因塗膜的乾燥不充分所造成的外觀不良之發生。The film thickness at the time of applying a general coating material to a base material is not particularly limited, and can be arbitrarily selected. For example, 1-200 micrometers are preferable, 10-150 micrometers are more preferable, 10-100 micrometers are especially preferable. When the film thickness of the general paint applied is 1 μm or more, a general processed product with good flame retardancy can be easily obtained. If the film thickness of a general coating material is 200 μm or less, the occurrence of poor appearance due to insufficient drying of the coating film can be suppressed.

作為使塗佈有一般塗料的基材乾燥之方法，可使用以往習知的方法。於使塗佈有一般塗料的基材乾燥時，亦可將塗佈有一般塗料的基材加熱。將塗佈有一般塗料的基材加熱而使其乾燥時的加熱溫度係可任意地選擇，但較佳為80℃～170℃，更佳為90℃～150℃。若上述加熱溫度為80℃以上，則藉由加熱所造成之促進塗佈有一般塗料的基材之乾燥。若上述加熱溫度為170℃以下，則因加熱所造成之塗佈有一般塗料的基材之劣化不易發生。A conventionally known method can be used as a method of drying a substrate coated with a general coating material. When drying the substrate coated with the general paint, the substrate coated with the general paint can also be heated. The heating temperature at the time of heating and drying the base material coated with a general coating material can be arbitrarily selected, but is preferably 80°C to 170°C, more preferably 90°C to 150°C. If the above-mentioned heating temperature is 80° C. or higher, drying of the substrate coated with a general coating material will be accelerated by heating. When the said heating temperature is 170 degrees C or less, the deterioration of the base material to which the general coating material was apply|coated by heating does not easily occur.

本實施形態之加工品的一般加工品具有優異的難燃性、抗滲出性及抗黏連性。又，本實施形態之一般加工品由於包含含有來自聚合性不飽和單體(B)的構成成分之共聚物，而塗膜與基材之密著性及外觀的安定性優異。基於此，本實施形態之一般加工品例如係可適合作為建築材料、電子材料、汽車內部裝飾材料用途之材料。The general processed product of the processed product of the present embodiment has excellent flame retardancy, anti-bleeding property and anti-blocking property. Moreover, since the general processed product of this embodiment contains the copolymer containing the structural component derived from the polymerizable unsaturated monomer (B), it is excellent in the adhesiveness of a coating film and a base material, and the stability of an external appearance. Based on this, the general processed product of this embodiment is suitable for use as a building material, an electronic material, and an automobile interior material, for example.

「黏接著劑及黏接著劑加工品」 (黏接著劑) 　　作為本實施形態之黏接著劑，可使用使本實施形態之共聚物溶解或分散於溶劑中者。　　本實施形態之黏接著劑中的共聚物之含量係可任意地選擇，但較佳為1～90質量%，更佳為10～80質量%。藉由成為共聚物之含量為上述範圍之黏接著劑，可更有效果地得到包含共聚物所致的效果。"Adhesives and Adhesive Products" (Adhesives) As the adhesives of the present embodiment, those in which the copolymer of the present embodiment is dissolved or dispersed in a solvent can be used. The content of the copolymer in the adhesive of the present embodiment can be arbitrarily selected, but is preferably 1 to 90% by mass, more preferably 10 to 80% by mass. By making it into the adhesive agent whose content of a copolymer is the said range, the effect by containing a copolymer can be acquired more effectively.

(黏接著劑加工品) 　　所謂本實施形態之黏接著劑加工品中的基材，就是藉由黏接著劑貼合的被黏體與支持包含黏接著劑的黏接著劑層之支持體中的至少1個。　　作為基材之材料，例如可舉出聚對苯二甲酸乙二酯等之聚酯；聚烯烴、聚醯胺、聚醯亞胺等之聚合物；天然或合成橡膠；紙；金屬；玻璃布等，不受此等所限定。　　於基材之表面，為了提高與附著於基材上之包含黏接著劑的黏接著劑層之密著性，可形成錨層，或施予電暈處理或電漿處理等的各種易接著處理。(Adhesive agent processed product) The so-called base material in the adhesive agent processed product of the present embodiment refers to the substrate in the adherend bonded by the adhesive agent and the support body supporting the adhesive agent layer containing the adhesive agent. At least 1. Examples of the base material include polyesters such as polyethylene terephthalate; polymers such as polyolefin, polyamide, and polyimide; natural or synthetic rubber; paper; metal; glass cloth etc., are not limited by these. On the surface of the substrate, in order to improve the adhesion with the adhesive layer containing the adhesive attached to the substrate, an anchor layer can be formed, or various easy-bonding treatments such as corona treatment or plasma treatment can be applied. .

作為支持體使用的基材，可舉出紙、塑膠薄膜、塑膠或橡膠的發泡體、金屬、玻璃、織布、不織布、無機板等。　　作為支持體使用的基材之形狀，較佳為薄膜狀或膠帶狀。　　於作為支持體使用的基材上塗佈黏接著劑，使其乾燥而形成黏接著劑層時，亦可在黏接著劑層上貼合以樹脂薄膜等所形成的剝離薄膜。As the base material used for the support, paper, plastic film, foam of plastic or rubber, metal, glass, woven fabric, non-woven fabric, inorganic board, etc. are mentioned. The shape of the substrate used as the support is preferably a film or tape. When an adhesive agent is applied to a substrate used as a support and dried to form an adhesive agent layer, a release film formed of a resin film or the like can also be pasted on the adhesive agent layer.

附著於基材上之包含共聚物的黏接著劑層之厚度(乾燥後之厚度)係可設為任意之厚度，可按照用途而適宜決定。具體而言，黏接著劑層之厚度較佳為5～200μm，更佳為10～150μm，尤佳為10～100μm。若黏接著劑層之厚度為5μm以上，則可容易得到難燃性良好的黏接著劑加工品。若黏接著劑層之厚度為200μm以下，則可得到黏接著劑充分地乾燥之黏接著劑層。The thickness (thickness after drying) of the adhesive layer containing the copolymer attached to the base material can be set to any thickness, and can be appropriately determined according to the application. Specifically, the thickness of the adhesive layer is preferably 5 to 200 μm, more preferably 10 to 150 μm, and particularly preferably 10 to 100 μm. When the thickness of the adhesive layer is 5 μm or more, a processed adhesive product with good flame retardancy can be easily obtained. When the thickness of the adhesive layer is 200 μm or less, an adhesive layer in which the adhesive is sufficiently dried can be obtained.

(黏接著劑加工品之製造方法) 　　作為本實施形態的黏接著劑加工品之製造方法，可無特別限制地採用以往習知的方法。　　基材係藉由黏接著劑貼合的被黏體時，例如可舉出於基材之被黏面，塗佈本實施形態之黏接著劑後，以接觸於由黏接著劑所構成的塗膜之方式，在基材配置要貼合的另一材料，使由黏接著劑所構成的塗膜乾燥之方法等。　　作為於藉由黏接著劑貼合的被黏體之基材，塗佈黏接著劑之方法，可使用以往習知的方法。例如，作為塗佈黏接著劑之方法，可舉出線棒、塗抹器、毛刷、噴霧、輥、凹版塗佈機、模塗機、唇塗機、缺角輪塗佈機、刀塗機、反向塗佈機、旋轉塗佈機等。(Manufacturing method of the adhesive agent product) As the manufacturing method of the adhesive agent processed product of this embodiment, a conventionally known method can be used without particular limitation. When the substrate is an adherend bonded by an adhesive, for example, it can be used on the adhered surface of the substrate. In the film method, another material to be bonded is placed on the base material, and the coating film composed of the adhesive is dried. As the method of applying the adhesive to the base material of the adherend to be bonded by the adhesive, a conventionally known method can be used. For example, as a method of applying the adhesive, a wire bar, an applicator, a brush, a spray, a roll, a gravure coater, a die coater, a lip coater, a notch coater, and a knife coater can be mentioned. , reverse coater, spin coater, etc.

基材為作為支持體使用的薄膜狀者時，例如可舉出在基材的單面或兩面，塗佈本實施形態之黏接著劑後，使其乾燥之方法等。藉此，可得到薄膜狀的黏接著劑加工品。又，藉由按照用途，捲取薄膜狀的黏接著劑加工品及切斷，可得到膠帶狀的黏接著劑加工品。　　於作為支持體使用的薄膜狀基材塗佈黏接著劑時，例如可使用輥塗、吻輥塗佈、輥刷、浸輥塗佈、棒塗、氣刀塗佈、簾式塗佈、模塗機等所致之擠出塗佈法等的塗佈方法。When the substrate is in the form of a film used as a support, for example, a method of applying the adhesive of the present embodiment to one or both surfaces of the substrate and then drying it may be mentioned. Thereby, a film-shaped adhesive agent processed product can be obtained. Moreover, by winding up and cutting the film-shaped adhesive agent processed product according to the application, a tape-shaped adhesive agent processed product can be obtained. When applying an adhesive to a film-like substrate used as a support, for example, roll coating, kiss roll coating, roll brush, dip roll coating, bar coating, air knife coating, curtain coating, die coating can be used. Coating methods such as extrusion coating methods caused by coating machines and the like.

作為使塗佈於基材上的黏接著劑乾燥之方法，可使用以往習知的方法。使塗佈有黏接著劑的基材乾燥時，亦可將塗佈有黏接著劑的基材加熱。將塗佈有黏接著劑的基材加熱而使其乾燥時的加熱溫度係可任意地選擇，但較佳為80℃～170℃，更佳為90℃～150℃。若上述加熱溫度為80℃以上，則藉由加熱而促進塗佈有黏接著劑的基材之乾燥。若上述加熱溫度為170℃以下，則塗佈有黏接著劑的基材之因加熱所致之劣化不易發生。As a method of drying the adhesive agent applied on the base material, a conventionally known method can be used. When drying the adhesive-coated substrate, the adhesive-coated substrate may be heated. The heating temperature at the time of heating and drying the base material coated with the adhesive can be arbitrarily selected, but is preferably 80°C to 170°C, more preferably 90°C to 150°C. When the said heating temperature is 80 degreeC or more, the drying of the base material to which the adhesive agent was apply|coated will be accelerated|stimulated by heating. When the said heating temperature is 170 degrees C or less, the deterioration by heating of the base material to which the adhesive agent was apply|coated is hard to generate|occur|produce.

於本實施形態中，於使塗佈有黏接著劑的基材乾燥而得的黏接著劑層之表面，亦可進行易接著處理。　　又，於黏接著劑層上，亦可貼合以樹脂薄膜等所形成的剝離薄膜。In this embodiment, the surface of the adhesive agent layer obtained by drying the base material to which the adhesive agent was applied may be subjected to an easy-adhesion treatment. In addition, a release film formed of a resin film or the like may be pasted on the adhesive layer.

本實施形態之加工品的黏接著劑加工品具有優異的難燃性、抗滲出性及抗黏連性，初期黏著力及耐熱保持力優異。基於此，本實施形態之黏接著劑加工品例如係可適用作為黏著膠帶、雙面膠帶、黏著標籤等之日用品、壁紙、地磚、地墊(緩衝地板)、地毯、天花板材料、窗用黏著片等之建築材料、汽車用製品、家電製品、電子零件等。The adhesive processed product of the processed product of the present embodiment has excellent flame retardancy, bleed resistance, and blocking resistance, and is excellent in initial adhesion and heat-resistant retention. Based on this, the adhesive processed product of the present embodiment can be applied to, for example, adhesive tapes, double-sided tapes, adhesive labels, etc. for daily necessities, wallpapers, floor tiles, floor mats (buffer floors), carpets, ceiling materials, and adhesive sheets for windows. and other building materials, automotive products, home appliances, electronic parts, etc.

[實施例][Example]

以下，藉由實施例及比較例，更具體地說明本發明。還有，本發明係不限定於僅以下之實施例。Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, this invention is not limited only to the following Example.

[樹脂組成物] (實施例1)[Resin composition] (Example 1)

均勻地混合表1所示之含磷不飽和單體(A)的酸性膦醯氧基乙基甲基丙烯酸酯100g、聚合性不飽和單體(B)之具有碳原子數及氧原子數之合計為4～10的主鏈之不飽和羧酸單體(b-1)的丙烯酸100g、具有碳數為1～4的烷基之(甲基)丙烯酸烷酯單體(b-2)的甲基丙烯酸酯0.5g、鏈轉移劑(C)的巰基丙酸4.0g、界面活性劑的十二基苯磺酸鈉1.5g及聚氧乙烯烷基醚7.5g、與作為溶劑的離子交換水150g，成為包含單體的溶液。Uniformly mixed 100 g of acidic phosphinodonoxyethyl methacrylate of the phosphorus-containing unsaturated monomer (A) shown in Table 1, and the polymerizable unsaturated monomer (B) having the number of carbon atoms and the number of oxygen atoms. 100 g of acrylic acid of unsaturated carboxylic acid monomer (b-1) having a total of 4 to 10 main chains, and alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms 0.5 g of methacrylate, 4.0 g of mercaptopropionic acid as a chain transfer agent (C), 1.5 g of sodium dodecylbenzenesulfonate as a surfactant, 7.5 g of polyoxyethylene alkyl ether, and ion-exchanged water as a solvent 150 g as a solution containing monomers.

於五口的可分離式燒瓶中，置入1L的作為溶劑的離子交換水150g，邊攪拌邊加熱到80℃。於上述的可分離式燒瓶中，添加起始劑的過硫酸鉀3.0g。然後，於上述的可分離式燒瓶中，開始滴下包含單體的溶液及10質量%過硫酸鉀水溶液，而開始聚合反應。包含單體的溶液係以大略一定的供給量，費4小時添加到可分離式燒瓶內。10質量%過硫酸鉀水溶液70g亦與包含單體的溶液一起，以大略一定的供給量，費4小時添加。於包含單體的溶液及10質量%過硫酸鉀水溶液之添加結束後，在80℃攪拌2小時，結束反應。In a 5-neck separable flask, 1 L of ion-exchanged water as a solvent was put in 150 g, and the mixture was heated to 80° C. while stirring. In the above-mentioned separable flask, 3.0 g of potassium persulfate as a starter was added. Then, in the above-mentioned separable flask, a solution containing a monomer and a 10 mass % potassium persulfate aqueous solution were started to be dripped, and a polymerization reaction was started. The monomer-containing solution was added to the separable flask in a roughly constant supply amount over 4 hours. 70 g of a 10 mass % potassium persulfate aqueous solution was also added together with the monomer-containing solution in a roughly constant supply amount over 4 hours. After the addition of the solution containing the monomer and the 10 mass % potassium persulfate aqueous solution was completed, the reaction was completed by stirring at 80° C. for 2 hours.

於反應結束後，冷卻可分離式燒瓶，添加中和劑的30質量%氫氧化鈉水溶液20g，而中和反應系內。於中和劑之添加結束後，攪拌1小時。藉由以上之步驟，得到實施例1之共聚物分散或溶解於水中之樹脂組成物。　　表1中顯示實施例1的樹脂組成物之製造中使用的原料及使用量。After the completion of the reaction, the separable flask was cooled, and 20 g of a 30 mass % aqueous sodium hydroxide solution as a neutralizing agent was added to neutralize the inside of the reaction system. After the addition of the neutralizer was completed, it was stirred for 1 hour. Through the above steps, the resin composition in which the copolymer of Example 1 was dispersed or dissolved in water was obtained. Table 1 shows the raw materials and usage amounts used in the manufacture of the resin composition of Example 1.

(實施例2～30、比較例1～8) 　　除了以表1～表6所示的使用量，使用表1～表6所示的原料以外，與實施例1同樣地，得到實施例2～30、比較例1～8之樹脂組成物。(Examples 2 to 30, Comparative Examples 1 to 8) Examples 2 to 2 were obtained in the same manner as in Example 1, except that the raw materials shown in Tables 1 to 6 were used in the amounts shown in Tables 1 to 6. 30. The resin compositions of Comparative Examples 1-8.

表1～表6中的各成分之詳細係如以下。 (含磷不飽和單體(A)) 　　酸性膦醯氧基乙基甲基丙烯酸酯(UNICHEMICAL股份有限公司製，Phosmer M，磷原子含量15質量%) 　　酸性膦醯氧基乙基丙烯酸酯(共榮社化學股份有限公司製，P-1A，磷原子含量16質量%) 　　二苯基-2-甲基丙烯醯氧基乙基磷酸酯(大八化學工業股份有限公司製，MR-260，磷原子含量8質量%) 　　酸性膦醯氧基聚氧乙烯二醇單甲基丙烯酸酯(UNICHEMICAL股份有限公司製，Phosmer PE，磷原子含量9質量%)The details of each component in Tables 1 to 6 are as follows. (Phosphorus-Containing Unsaturated Monomer (A)) Acidic Phosphonodonoxyethyl Methacrylate (Unichemical Co., Ltd., Phosmer M, Phosphorus Atom Content: 15% by Mass) Acidic Phosphonooxyethylacrylate (Co- Eisha Chemical Co., Ltd. product, P-1A, phosphorus atom content 16% by mass) Diphenyl-2-methacryloyloxyethyl phosphate (Daihachi Chemical Industry Co., Ltd. product, MR-260, phosphorus Atomic content of 8 mass %) Acid phosphinodioxy polyoxyethylene glycol monomethacrylate (UNICHEMICAL Co., Ltd., Phosmer PE, phosphorus atom content of 9 mass %)

(聚合性不飽和單體(B)) 　　(具有碳原子數及氧原子數之合計為4～10的主鏈之不飽和羧酸單體(b-1)) 　　丙烯酸(三菱化學股份有限公司製) 　　甲基丙烯酸(三菱瓦斯化學股份有限公司製) 　　伊康酸(扶桑化學工業股份有限公司製) 　　β-羧基乙基丙烯酸(DAICEL-ALLNEX股份有限公司製)(Polymerizable unsaturated monomer (B)) (Unsaturated carboxylic acid monomer (b-1) having a main chain having a total of 4 to 10 carbon atoms and oxygen atoms) Acrylic acid (manufactured by Mitsubishi Chemical Corporation) ) Methacrylic acid (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Iconic acid (manufactured by Fuso Chemical Industry Co., Ltd.) β-carboxyethyl acrylic acid (manufactured by DAICEL-ALLNEX Co., Ltd.)

(具有碳數為1～4的烷基之(甲基)丙烯酸烷酯單體(b-2)) 　　甲基丙烯酸酯(東亞合成股份有限公司製) 　　丙烯酸乙酯(東亞合成股份有限公司製) 　　丙烯酸丁酯(東亞合成股份有限公司製) 　　甲基丙烯酸甲酯(三菱瓦斯化學股份有限公司製) 　　(其他的(B)) 　　2-丙烯醯氧基乙基-琥珀酸(共榮社化學股份有限公司製)(Alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms) Methacrylate (manufactured by Toagosei Co., Ltd.) Ethyl acrylate (manufactured by Toagosei Co., Ltd.) Butyl acrylate (manufactured by Toagosei Co., Ltd.) Methyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) (Other (B)) 2-Propenyloxyethyl-succinic acid (Kyoeisha Chemical Co., Ltd. company system)

(鏈轉移劑(C)) 　　β-巰基丙酸(股份有限公司同仁化學研究所製) 巰基乙酸2-乙基己酯(東京化成工業股份有限公司製)(Chain transfer agent (C)) β-Mercaptopropionic acid (manufactured by Dojin Chemical Research Institute Co., Ltd.) 2-ethylhexyl thioglycolate (manufactured by Tokyo Chemical Industry Co., Ltd.)

(界面活性劑) 　　十二基苯磺酸鈉(花王股份有限公司製) 　　聚氧乙烯月桂基醚(花王股份有限公司製) 聚乙烯醇(股份有限公司KURARAY製，PVA205(皂化度86.5～89.0%，平均聚合度500))(Surfactant) Sodium dodecylbenzenesulfonate (manufactured by Kao Co., Ltd.) Polyoxyethylene lauryl ether (manufactured by Kao Co., Ltd.) Polyvinyl alcohol (manufactured by KURARAY Co., Ltd., PVA205 (degree of saponification 86.5-89.0%) , the average degree of polymerization 500))

(起始劑) 　　過硫酸鉀(三菱瓦斯化學股份有限公司製) 　　過硫酸銨(三菱瓦斯化學股份有限公司製) 　　偶氮雙異丁腈(大塚化學股份有限公司製)(Starter) Potassium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Azobisisobutyronitrile (manufactured by Otsuka Chemical Co., Ltd.)

(中和劑) 　　30質量%氫氧化鈉水溶液(KISHIDA化學股份有限公司製)25質量%氨水溶液(宇部興產股份有限公司製) 　　單甲基胺(三菱瓦斯化學股份有限公司製)(Neutralizing agent) 30 mass % sodium hydroxide aqueous solution (manufactured by Kishida Chemical Co., Ltd.) 25 mass % ammonia aqueous solution (manufactured by Ube Industries Co., Ltd.) Monomethylamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

(溶劑) 　　二乙二醇單乙基醚(東京化成工業股份有限公司製)(Solvent) Diethylene glycol monoethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

「磷原子含量」　　表1～表6中的不飽和單體成分中之磷原子含量係藉由以下之式算出。表1～表6中顯示其結果。所算出的磷原子含量係可視為相對於實施例1～30、比較例1～8的各共聚物之磷原子含量。　　磷原子含量(質量%)=[含磷不飽和單體(A)中的磷原子之質量/含磷不飽和單體(A)與聚合性不飽和單體(B)之合計質量]×100"Phosphorus Atom Content" The phosphorus atom content in the unsaturated monomer components in Tables 1 to 6 was calculated by the following formula. The results are shown in Tables 1 to 6. The calculated phosphorus atom content can be regarded as the phosphorus atom content with respect to each of the copolymers of Examples 1 to 30 and Comparative Examples 1 to 8. Phosphorus atom content (mass %)=[mass of phosphorus atoms in phosphorus-containing unsaturated monomer (A)/total mass of phosphorus-containing unsaturated monomer (A) and polymerizable unsaturated monomer (B)]×100

藉由去除實施例1～30、比較例1～8的各樹脂組成物中之溶劑的水而使其乾燥，從樹脂組成物中分離包含共聚物的樹脂固體成分。　　然後，針對實施例1～30、比較例1～8的樹脂組成物或樹脂固體成分，藉由以下所示的評價方法進行評價。表1～表8中顯示其結果。The resin solid content containing the copolymer was separated from the resin composition by removing water from the solvent in the resin compositions of Examples 1 to 30 and Comparative Examples 1 to 8 and drying them. Next, the resin compositions or resin solid content of Examples 1 to 30 and Comparative Examples 1 to 8 were evaluated by the following evaluation methods. The results are shown in Tables 1 to 8.

「質量平均分子量」　　於以下之條件下使用凝膠滲透層析術(GPC)：商品名「Shodex GPC-101」(昭和電工股份有限公司製，「Shodex」為註冊商標)，測定共聚物之質量平均分子量。　　調製於磷酸氫二鈉12水合物34.5g及磷酸二氫鈉2水合物46.2g中，加入超純水而使全量成為5.000g的水溶液，作為載液。於此載液中溶解包含共聚物的樹脂固體成分，使用泵(＜DU-H2000＞，Shodex製)，以流速0.5ml/min.進行測定。"Mass average molecular weight" The mass of the copolymer was measured using gel permeation chromatography (GPC) under the following conditions: trade name "Shodex GPC-101" (manufactured by Showa Denko Co., Ltd., "Shodex" is a registered trademark) average molecular weight. Prepared in 34.5 g of disodium hydrogen phosphate dihydrate and 46.2 g of sodium dihydrogen phosphate dihydrate, and added ultrapure water to make an aqueous solution of 5.000 g in total, as a carrier liquid. The resin solid content containing the copolymer was dissolved in this carrier liquid, and the measurement was performed at a flow rate of 0.5 ml/min. using a pump (<DU-H2000>, manufactured by Shodex).

作為管柱，使用水系GPC管柱(分析管柱：＜OHpak SB-806M MQ＞，Shodex製，參考管柱：＜OHpak SB-800RL＞，Shodex製)，作為檢測器，使用RI檢測器(＜RI-71S＞，Shodex製)。作為分子量標準樣品，使用聚丙烯酸鈉(Sigma-Aldrich)。As the column, an aqueous GPC column (analytical column: <OHpak SB-806M MQ>, manufactured by Shodex, reference column: <OHpak SB-800RL>, manufactured by Shodex) was used, and as the detector, an RI detector (< RI-71S>, manufactured by Shodex). As a molecular weight standard sample, sodium polyacrylate (Sigma-Aldrich) was used.

「酸價」　　共聚物之酸價係依據JIS K 0070之中和滴定法，如以下般進行而予以評價。　　使用精密天平，精秤約2g的試料(包含共聚物的樹脂固體成分)，置入100ml三角燒瓶中，於其中加入乙醇/二乙基醚=1/1(質量比)之混合溶劑10ml及溶解。再者，於此三角燒瓶中，添加1～3滴作為指示劑的酚酞乙醇溶液，充分地攪拌直到試料成為均勻為止。以0.1N氫氧化鉀-乙醇溶液滴定此，將指示劑的淡紅色持續30秒時，作為中和之終點。由其結果，將使用下述式(5)而得之值作為共聚物的酸價。"Acid value" The acid value of the copolymer was evaluated by neutralization titration according to JIS K 0070 as follows. Using a precision balance, accurately weigh about 2g of the sample (containing the resin solid content of the copolymer), put it into a 100ml conical flask, add 10ml of a mixed solvent of ethanol/diethyl ether=1/1 (mass ratio) and dissolve it. . In addition, 1 to 3 drops of a phenolphthalein ethanol solution as an indicator is added to this Erlenmeyer flask, and the mixture is sufficiently stirred until the sample becomes uniform. This was titrated with a 0.1N potassium hydroxide-ethanol solution, and when the light red color of the indicator continued for 30 seconds, it was regarded as the end point of neutralization. From the results, the value obtained by using the following formula (5) was used as the acid value of the copolymer.

酸價(mgKOH/g)=(B´f´5.611)/S (5) 　　B：0.1N氫氧化鉀-乙醇溶液的使用量(ml) 　　f：0.1N氫氧化鉀-乙醇溶液的因數　　S：試料的採集量(g)Acid value (mgKOH/g)=(B´f´5.611)/S (5) B: Amount of 0.1N potassium hydroxide-ethanol solution used (ml) f: Factor S of 0.1N potassium hydroxide-ethanol solution: Sample collection amount (g)

(難燃性) 　　將以藉由後述方法所製作之樹脂薄膜，於23℃、相對濕度50%之條件下靜置12小時以上，作為試驗體。接著，從試驗體採集長度150mm、寬度60mm的試驗片。然後，依據JIS K 7201-2：1999之方法，將試驗片安裝於U字形保持具，分別測定著火後的試驗片持續燃燒長度50mm燃燒所需要的最低氧濃度，及燃燒時間成為180秒以上所需要的最低氧濃度，將值為小者作為氧指數。作為燃燒性的指標，將氧指數22%以下者作為可燃性，將氧指數23～27%者作為自熄性，將氧指數28%以上者作為難燃性。　　○(良)：氧指數50%以上　　△(可)：氧指數40%以上～未達50% 　　´(不行)：氧指數未達40%(Flammability) The resin film produced by the method described later was allowed to stand for more than 12 hours under the conditions of 23°C and 50% relative humidity as a test body. Next, a test piece having a length of 150 mm and a width of 60 mm was collected from the test body. Then, according to the method of JIS K 7201-2:1999, the test piece was mounted on the U-shaped holder, and the minimum oxygen concentration required for the continuous burning length of 50mm burning of the test piece after ignition was measured, and the burning time was 180 seconds or more. The minimum oxygen concentration required, and the smaller value is used as the oxygen index. As an index of flammability, those with an oxygen index of 22% or less were regarded as flammable, those with an oxygen index of 23 to 27% were regarded as self-extinguishing properties, and those with an oxygen index of 28% or more were regarded as flame retardancy. ○(Good): Oxygen index is more than 50% △(Yes): Oxygen index is more than 40% to less than 50% ´(No): Oxygen index is less than 40%

＜樹脂薄膜之製作＞　　將實施例1～30、比較例1～8之樹脂組成物，分別使用離子交換水稀釋為固體成分成為20質量%，作為樹脂薄膜製作用的樹脂液。將該樹脂液均勻地流入於以矽密封膠所製作之長：200mm、寬：50mm的框內而成為玻璃板狀。確認流入樹脂液的玻璃板為水平，以真空乾燥機於70℃乾燥24小時，得到實施例1～30、比較例1～8之樹脂薄膜。<Preparation of resin film> The resin compositions of Examples 1 to 30 and Comparative Examples 1 to 8 were diluted with ion-exchanged water so that the solid content was 20% by mass, and used as resin liquids for resin film production. The resin liquid was uniformly poured into a frame made of silicone sealant with a length of 200 mm and a width of 50 mm to form a glass plate. It was confirmed that the glass plate into which the resin liquid had flowed was horizontal, and it was dried at 70° C. with a vacuum dryer for 24 hours to obtain resin films of Examples 1 to 30 and Comparative Examples 1 to 8.

(保存安定性) 　　將pH變化作為確認保存安定性之指標。針對剛製造的樹脂組成物，測定在23℃的pH。又，於容量140mL的無色透明之玻璃瓶中，填充剛製造的樹脂組成物直到容量的90%體積為止及密閉，於23℃、相對濕度50%之條件下保管半年。然後，針對半年保管後的樹脂組成物，測定在23℃的pH。其後，依照以下所示的標準，評價剛製造的樹脂組成物與半年間保管後的樹脂組成物之pH變化量。「基準」　　○(良)：pH變化量為±0～未達2 　　△(可)：pH變化量為±2.0以上～未達3 　　´(不行)：pH變化量±3.0以上(Storage stability) The pH change is used as an index to confirm the storage stability. About the resin composition just produced, pH at 23 degreeC was measured. In addition, a colorless and transparent glass bottle with a capacity of 140 mL was filled with the resin composition just produced until the volume reached 90% of the volume, sealed, and stored at 23° C. and a relative humidity of 50% for half a year. Then, the pH at 23°C was measured for the resin composition after storage for half a year. Then, the amount of pH change of the resin composition immediately after production and the resin composition after storage for half a year was evaluated according to the criteria shown below. "Standard" ○ (good): pH change is ±0 to less than 2 △ (good): pH change is more than ±2.0 to less than 3 ´ (not possible): pH change is ±3.0 or more

(聚合安定性) 　　依據剛製造的樹脂組成物中之殘存單體量(所使用的全部不飽和單體成分之中，殘存在樹脂組成物中的不飽和單體成分之含量)及聚合時有無凝膠化，用以下所示的標準進行評價。殘存單體量係藉由氣體層析法測定。「基準」　　○(良)：未凝膠化，且殘存單體為0%以上～未達0.1質量% 　　△(可)：未凝膠化，且殘存單體為0.1%以上～未達1質量% 　　´(不行)：因凝膠化而聚合中止，或殘存單體為1質量%以上(Polymerization stability) According to the amount of residual monomers in the resin composition just produced (out of all the unsaturated monomer components used, the content of unsaturated monomer components remaining in the resin composition) and the presence or absence of polymerization Gelation was evaluated by the criteria shown below. The residual monomer amount was measured by gas chromatography. "Standard" ○ (Good): Not gelled, and the residual monomer is 0% or more to less than 0.1% by mass % ´ (not possible): The polymerization was terminated due to gelation, or the residual monomer was 1% by mass or more

如表7所示，使用實施例1～30之樹脂組成物所製造的樹脂薄膜係難燃性良好。其中，包含鏈轉移劑(C)的實施例1～27之樹脂組成物係保存安定性及聚合安定性特別良好。又，實施例1～27之樹脂組成物係保存安定性特別良好。As shown in Table 7, the resin films produced using the resin compositions of Examples 1 to 30 were excellent in flame retardancy. Among them, the resin compositions of Examples 1 to 27 containing the chain transfer agent (C) were particularly good in storage stability and polymerization stability. In addition, the resin compositions of Examples 1 to 27 have particularly good storage stability.

如表8所示，使用不含含磷不飽和單體(A)的比較例1、具有碳數為1～4的烷基之(甲基)丙烯酸烷酯單體(b-2)多的比較例2、5～8、不含具有碳原子數及氧原子數之合計為4～10的主鏈之不飽和羧酸單體(b-1)之比較例3之樹脂組成物所製造的樹脂薄膜，係難燃性不良。　　又，不含不飽和羧酸單體(b-1)的比較例4之樹脂組成物係聚合安定性顯著地低，無法進行難燃性及保存安定性之評價。As shown in Table 8, Comparative Example 1 which does not contain phosphorus-containing unsaturated monomer (A), and alkyl (meth)acrylate monomer (b-2) having a carbon number of 1 to 4 alkyl groups were used. Comparative Examples 2, 5 to 8, and the resin composition of Comparative Example 3 which did not contain the unsaturated carboxylic acid monomer (b-1) having a main chain having a total number of carbon atoms and oxygen atoms of 4 to 10 The resin film has poor flame retardancy. In addition, the resin composition of Comparative Example 4, which does not contain the unsaturated carboxylic acid monomer (b-1), has remarkably low polymerization stability, and the evaluation of flame retardancy and storage stability cannot be performed.

「紙加工品・纖維加工品」 (實施例31～33、35～37、比較例9、10) 　　以表9、表10所示之比例，摻合表9、表10所示的樹脂與稀釋劑的水，調製實施例31～33、35～37、比較例9、10所用之處理劑1～4。　　表9、表10所示的「樹脂1」表示實施例1之樹脂組成物，「樹脂3」表示實施例3之樹脂組成物，「樹脂5」表示實施例5之樹脂組成物，「樹脂28」表示比較例1之樹脂組成物。"Paper processed products and fiber processed products" (Examples 31 to 33, 35 to 37, Comparative Examples 9 and 10) The resins shown in Tables 9 and 10 were blended and diluted at the ratios shown in Tables 9 and 10. The water of the agent was used to prepare the treatment agents 1 to 4 used in Examples 31 to 33, 35 to 37, and Comparative Examples 9 and 10. "Resin 1" shown in Tables 9 and 10 indicates the resin composition of Example 1, "Resin 3" indicates the resin composition of Example 3, "Resin 5" indicates the resin composition of Example 5, "Resin 28" indicates the resin composition of Example 5 " represents the resin composition of Comparative Example 1.

(實施例34、38) 　　以表9、表10所示的比例，摻合表9、表10所示的樹脂、難燃劑的聚磷酸銨(Clariant Chemicals股份有限公司製，Exolit AP422，磷原子含量32質量%)與稀釋劑的水，調製實施例34、38所使用之處理劑5。(Examples 34 and 38) Ammonium polyphosphate (Exolit AP422, manufactured by Clariant Chemicals Co., Ltd., manufactured by Clariant Chemicals Co., Ltd., phosphorus atom Content 32 mass %) and the water of the diluent to prepare the treatment agent 5 used in Examples 34 and 38.

使用如此般進行所得之處理劑1～5作為紙處理劑，以後述之方法製作實施例31～34、比較例9之紙加工品。又，使用處理劑1～5作為纖維處理劑，以後述之方法製作實施例35～38、比較例10之纖維加工品。The processing agents 1 to 5 obtained in this way were used as paper processing agents, and the processed paper products of Examples 31 to 34 and Comparative Example 9 were produced by the method described later. Moreover, using the processing agents 1-5 as a fiber processing agent, the fiber processed goods of Examples 35-38 and Comparative Example 10 were produced by the method mentioned later.

＜紙加工品之製作＞　　作為基材，準備濾紙(No.2東洋濾紙股份有限公司製，厚度0.25mm，單位面積重量130g/m² )。然後，使表9所示的處理劑1～5浸漬於基材及塗佈。其後，以2支軋液輥壓榨已含浸處理劑的基材，使處理劑附著於1～5基材。接著，以熱風式乾燥機，使附著有處理劑的基材於130℃乾燥10分鐘，得到紙加工品。<Preparation of processed paper product> As a base material, filter paper (No. 2 Toyo Filter Paper Co., Ltd. product, thickness 0.25 mm, basis weight 130 g/m ² ) was prepared. Then, the treatment agents 1 to 5 shown in Table 9 were immersed in the substrate and applied. After that, the base material impregnated with the treatment agent was squeezed with two nip rolls, and the treatment agent was adhered to the base materials 1 to 5. Next, the base material to which the treatment agent adhered was dried at 130° C. for 10 minutes with a hot air dryer to obtain a paper processed product.

然後，針對所得之紙加工品，藉由以下所示的方法，求出相對於紙加工品之紙處理劑(處理劑)之固體成分量(質量%)。表9中顯示其結果。Then, about the obtained paper processed product, the solid content amount (mass %) of the paper processing agent (processing agent) with respect to the paper processed product was calculated|required by the method shown below. The results are shown in Table 9.

使用感度0.5mg以下的直讀天平，精秤處理劑浸漬前之基材。又，將浸漬有處理劑的基材在經調整成內溫105℃±2℃的乾燥機內放置1小時而使其乾燥。將乾燥後的基材在乾燥器內冷卻到室溫為止，以相同的直讀天平精秤，作為浸漬處理劑而經乾燥的基材(加工品)之質量。使用如此般進行所得之「加工品的質量」與「處理劑塗佈前之基材的質量」，以下式算出相對於加工品之處理劑之固體成分量(質量%)。　　相對於加工品之處理劑之固體成分量(質量%)={(加工品的質量-處理劑浸漬前之基材的質量)/(加工品的質量)}´100Use a direct-reading balance with a sensitivity of 0.5 mg or less to precisely weigh the substrate before immersion with the treatment agent. Moreover, the base material impregnated with the treatment agent was left to stand in a dryer adjusted to an internal temperature of 105° C.±2° C. for 1 hour to be dried. The dried base material was cooled to room temperature in a desiccator, and the mass of the base material (processed product) dried as an immersion treatment agent was measured with the same direct-reading balance. Using the "quality of the processed product" and "the mass of the base material before coating of the processing agent" obtained in this way, the solid content amount (mass %) of the processing agent with respect to the processed product was calculated by the following formula. The solid content of the treatment agent relative to the processed product (mass %) = {(the mass of the processed product - the mass of the substrate before the treatment agent is dipped)/(the mass of the processed product)}´100

＜纖維加工品之製作＞　　除了作為基材，使用由聚酯-纖維素不織布(股份有限公司BERKSHIRE製，厚度200μm，單位面積重量35g/m² )所構成的纖維以外，藉由與紙加工品同樣之方法，得到纖維加工品。　　然後，針對所得之纖維加工品，藉由與紙加工品同樣之方法，求出相對於纖維加工品之纖維處理劑(處理劑)之固體成分量(質量%)。表10中顯示其結果。<Production of processed fiber product> Except for using a fiber made of polyester-cellulose nonwoven fabric (manufactured by Berkshire Co., Ltd., thickness 200 μm, basis weight 35 g/m ² ) as the base material, and paper processed product In the same way, a fiber processed product was obtained. Then, the solid content amount (mass %) of the fiber processing agent (processing agent) with respect to the fiber processed product was calculated|required about the obtained fiber processed product by the method similar to the paper processed product. The results are shown in Table 10.

針對實施例31～34、比較例9之紙加工品、實施例35～38、比較例10之纖維加工品，藉由以下所示的評價方法，評價難燃性、抗滲出性、抗黏連性、硬挺性。表9、表10中顯示其結果。With respect to the processed paper products of Examples 31 to 34 and Comparative Example 9, and the processed fiber products of Examples 35 to 38 and Comparative Example 10, the following evaluation methods were used to evaluate flame retardancy, bleed resistance, and blocking resistance. Sex, stiffness. The results are shown in Table 9 and Table 10.

(難燃性) 　　將於23℃、相對濕度50%之條件下靜置12小時以上的紙加工品或纖維加工品作為試驗體，從各試驗體各自採集各5條長度127mm、寬度12.7mm之長條狀試驗片。對於各試驗片，基於據UL-94垂直燃燒試驗(V-0、V-1、V-2規格)，進行燃燒試驗。對於各試驗片，進行各2次(對於各試驗體，合計各10次)接觸火焰，測定熄焰時間(燃燒時間)。　　使用其結果，對於每試驗體，求出合計10次的接觸火焰所致的合計燃燒時間與最大燃燒時間，依照以下所示的標準進行評價。(Flammability) Paper processed products or fiber processed products that have been left standing at 23°C and relative humidity of 50% for more than 12 hours were used as test objects. Long strip test piece. For each test piece, a burning test was performed based on the vertical burning test according to UL-94 (V-0, V-1, and V-2 specifications). For each test piece, contact with the flame was performed twice (for each test body, 10 times in total), and the flame extinction time (burning time) was measured. Using the results, the total burning time and the maximum burning time due to a total of 10 contact flames were obtained for each test body, and evaluated according to the criteria shown below.

「基準」　　V-0：合計燃燒時間為50秒以內，且最大燃燒時間為10秒以內，於全部的試驗片中，沒有因燃燒所致的材料之滴下。　　V-1：合計燃燒時間為250秒以內，且最大燃燒時間為30秒以內，於全部的試驗片中，沒有因燃燒所致的材料之滴下。　　V-2：合計燃燒時間為250秒以內，且最大燃燒時間為30秒以內，但有因燃燒而材料滴下的試驗片。"Standard" V-0: The total burning time is within 50 seconds, the maximum burning time is within 10 seconds, and there is no dripping of material due to burning in all test pieces. V-1: The total burning time is within 250 seconds, the maximum burning time is within 30 seconds, and there is no material dripping due to burning in all test pieces. V-2: The total burning time is within 250 seconds, and the maximum burning time is within 30 seconds, but there are test pieces where material drips due to burning.

(抗滲出性) 　　從與難燃性之評價中使用者相同的試驗體，採集長70mm、寬50mm的矩形試驗片。於長100mm、寬60mm的矩形濾紙(No.2，東洋濾紙股份有限公司製)之間夾入試驗片，於60℃、相對濕度95%之條件下靜置5日，確認試驗片表面有無滲出。依照以下所示的標準，評價其結果。「基準」　　´(不行)：試驗片表面之白化係以試驗片面積之10%以上發生。　　△(可)：試驗片表面之白化係以未達試驗片面積之10%發生。　　○(良)：無試驗片表面之白化。(Bleed-out resistance) A rectangular test piece of 70 mm in length and 50 mm in width was collected from the same test body used in the evaluation of flame retardancy. A test piece was sandwiched between rectangular filter papers (No. 2, manufactured by Toyo Filter Paper Co., Ltd.) with a length of 100 mm and a width of 60 mm, and the test piece was allowed to stand for 5 days under the conditions of 60° C. and relative humidity of 95%, and the surface of the test piece was checked for exudation. . The results were evaluated according to the criteria shown below. "Standard" ´(No): The whitening of the surface of the test piece occurs at 10% or more of the area of the test piece. △ (possible): The whitening of the surface of the test piece occurs when it does not reach 10% of the area of the test piece. ○ (good): No whitening on the surface of the test piece.

(抗黏連性) 　　從與難燃性之評價中使用者相同的試驗體，採集長25mm、寬25mm的略正方形試驗片。於長35mm、寬35mm的略正方形底紙(合股公司柳生印刷所製)之間夾入試驗片，於60℃、相對濕度70%之條件下靜置3日，確認試驗片有無黏連。依照以下所示的標準，評價其結果。還有，從試驗片剝離底紙時是否發生聲音，係於23℃、300mm/min之條件下依據T型剝離試驗(Tensilon：ORIENTEC製RTA-100)進行剝離試驗，藉由評價當時有無剝離聲音之方法而判斷。(Blocking resistance) From the same test body used in the evaluation of flame retardancy, a roughly square test piece of 25 mm in length and 25 mm in width was collected. A test piece was sandwiched between slightly square base papers (manufactured by Yagyu Printing Co., Ltd., a joint stock company) with a length of 35 mm and a width of 35 mm. The results were evaluated according to the criteria shown below. In addition, whether or not a sound is generated when the backing paper is peeled from the test piece, the peeling test is performed according to the T-type peeling test (Tensilon: RTA-100 manufactured by ORIENTEC) under the conditions of 23° C. and 300 mm/min, and the presence or absence of peeling sound at that time is evaluated. method to judge.

「基準」　　´(不行)：從試驗片剝離底紙時發生聲音，且在從試驗片剝離的底紙上有剝屑(黏連有) 　　△(可)：從試驗片剝離底紙時發生聲音，但在從試驗片剝離的底紙上無剝屑(稍微有黏連) 　　○(良)：從試驗片剝離底紙時沒有發生聲音，且在從試驗片剝離的底紙上無剝屑(黏連無)"Standard" ´(No): A sound occurs when the backing paper is peeled from the test piece, and there is peeling (sticking) on the backing paper peeled from the test piece However, there is no peeling on the backing paper peeled from the test piece (slight blocking) ○ (good): No sound occurs when the backing paper is peeled from the test piece, and no peeling on the backing paper peeled from the test piece (no sticking). )

(硬挺性) 　　從與難燃性之評價中使用者相同的試驗體，採集長150mm、寬150mm的略正方形試驗片。將試驗片，依據JIS L1096：2010之一般織物試驗方法中記載的8.21.5E法(織物手感測定法)，進行硬挺性之測定。依照以下所示的標準，評價其結果。　　硬挺性(g)表示纖維的硬度(柔軟度)，硬挺性之數值愈高，表示試驗片之手感愈硬。「基準」　　○(良)：160g以上　　△(可)：140g以上～未達160g 　　´(不行)：未達140g(Stiffness) From the same test body used in the evaluation of flame retardancy, a roughly square test piece of 150 mm in length and 150 mm in width was collected. The test piece was subjected to the measurement of stiffness according to the 8.21.5E method (fabric texture measurement method) described in the general fabric testing method of JIS L1096:2010. The results were evaluated according to the criteria shown below. Stiffness (g) represents the hardness (softness) of the fiber, and the higher the stiffness value, the harder the test piece feels. "Standard" ○ (good): 160g or more △ (ok): 140g or more to less than 160g ´ (no): less than 140g

如表9、表10所示，實施例31～34之紙加工品及實施例35～38之纖維加工品係難燃性良好。又，實施例31～34之紙加工品及實施例35～38之纖維加工品係抗滲出性、抗黏連性、硬挺性皆「○(良)」或「△(可)」之評價而良好。　　相對於其，比較例9之紙加工品由於作為紙處理劑使用的處理劑4不含來自(A)的構成成分，而難燃性不良。又，比較例10之纖維加工品由於作為纖維處理劑使用的處理劑4不含來自(A)的構成成分，而難燃性不良。As shown in Table 9 and Table 10, the paper processed products of Examples 31 to 34 and the fiber processed products of Examples 35 to 38 were excellent in flame retardancy. In addition, the paper processed products of Examples 31 to 34 and the fiber processed products of Examples 35 to 38 were evaluated by the evaluation of "○ (good)" or "△ (fair)" in anti-bleeding property, blocking resistance, and stiffness. good. On the other hand, since the processing agent 4 used as a paper processing agent does not contain the structural component derived from (A), the paper processed product of the comparative example 9 is inferior in flame retardance. Moreover, since the processing agent 4 used as a fiber processing agent does not contain the structural component derived from (A), the fiber processed product of the comparative example 10 was inferior in flame retardance.

於實施例31～38之中，不使用磷系化合物的聚磷酸銨作為難燃劑的實施例31～33之紙加工品及實施例35～37之纖維加工品，係尤其抗滲出性及抗黏連性良好。In Examples 31 to 38, the paper processed products of Examples 31 to 33 and the fiber processed products of Examples 35 to 37, which do not use ammonium polyphosphate of phosphorus-based compound as the flame retardant, are particularly resistant to exudation and resistance. Good adhesion.

「一般加工品」 (實施例39～41、比較例11) 　　以表11所示的比例，摻合表11所示的樹脂與交聯劑的季戊四醇聚環氧丙基醚(Nagase ChemteX股份有限公司製，Denacol EX411)，調製實施例39～41、比較例11所用之塗料6～9。　　表11所示的「樹脂1」表示實施例1之樹脂組成物，「樹脂3」表示實施例3之樹脂組成物，「樹脂5」表示實施例5之樹脂組成物，「樹脂28」表示比較例1之樹脂組成物。"General processed products" (Examples 39 to 41, Comparative Example 11) Pentaerythritol polyglycidyl ether (Nagase ChemteX Co., Ltd.) was blended with the resin and crosslinking agent shown in Table 11 at the ratio shown in Table 11. Coatings 6-9 used in Examples 39-41 and Comparative Example 11 were prepared. "Resin 1" shown in Table 11 represents the resin composition of Example 1, "Resin 3" represents the resin composition of Example 3, "Resin 5" represents the resin composition of Example 5, and "Resin 28" represents the comparison The resin composition of Example 1.

(實施例42) 　　以表11所示的比例，摻合表11所示的樹脂、難燃劑的聚磷酸銨(Clariant Chemicals股份有限公司製，Exolit AP422，磷原子含量32質量%)與表11所示的交聯劑，調製實施例42所用之塗料10。(Example 42) At the ratio shown in Table 11, the resin shown in Table 11 and ammonium polyphosphate (Exolit AP422, phosphorus atom content: 32 mass %, manufactured by Clariant Chemicals Co., Ltd.; Coating 10 used in Example 42 was prepared using the indicated crosslinking agent.

使用如此般進行所得之塗料6～10，以後述之方法製作實施例39～42、比較例11之一般加工品。Using the paints 6 to 10 thus obtained, general processed products of Examples 39 to 42 and Comparative Example 11 were produced by the method described later.

＜一般加工品之製作＞　　作為基材，準備厚度25μm的PET薄膜。然後，以乾燥後之厚度成為10μm之方式，將表11所示之塗料6～10塗佈於基材。其後，以熱風式乾燥機，將塗佈有塗料的基材於105℃乾燥3分鐘，藉由於40℃熟化3日，得到一般加工品。<Production of general processed products> As a base material, a PET film with a thickness of 25 μm was prepared. Then, the coating materials 6-10 shown in Table 11 were apply|coated to a base material so that the thickness after drying might become 10 micrometers. Then, the base material applied with the coating material was dried at 105° C. for 3 minutes with a hot air dryer, and aged at 40° C. for 3 days to obtain a general processed product.

然後，針對所得之一般加工品，藉由與紙加工品同樣之方法，求出相對於一般加工品之塗料(處理劑)之固體成分量(質量%)。表11中顯示其結果。　　針對實施例39～42、比較例11之一般加工品，藉由以下所示的評價方法，評價難燃性、密著性、外觀變化。表11中顯示其結果。Then, with respect to the obtained general processed product, the solid content (mass %) of the coating material (treatment agent) with respect to the general processed product was determined by the same method as that of the paper processed product. The results are shown in Table 11. For the general processed products of Examples 39 to 42 and Comparative Example 11, flame retardancy, adhesion, and appearance changes were evaluated by the following evaluation methods. The results are shown in Table 11.

(難燃性) 　　分別使用一般加工品中使用的塗料6～10，與上述＜樹脂薄膜之作成＞同樣地製作薄膜，與使用樹脂組成物所作成的樹脂薄膜同樣地，評價一般加工品的難燃性。(Flammability) Coatings 6 to 10 used in general processed products were used, respectively, and films were produced in the same manner as in the above <Preparation of resin film>, and similarly to the resin films produced using the resin composition, the difficulty of general processed products was evaluated. flammability.

(密著性) 　　將於23℃、相對濕度50%之條件下靜置12小時以上的一般加工品作為試驗體，對於各試驗體，實施Cellotape(註冊商標)剝離試驗。藉由目視觀察剝離試驗後的一般加工品之表面，依照以下所示的標準進行評價。「基準」　　○(良)：無剝離　　△(可)：剝離的面積未達表面之80% 　　´(不行)：剝離的面積為表面之80%以上(Adhesion) A general processed product left standing at 23°C and a relative humidity of 50% for 12 hours or more was used as a test body, and a Cellotape (registered trademark) peeling test was performed for each test body. The surface of the general processed product after the peeling test was visually observed and evaluated according to the criteria shown below. "Standard" ○(Good): No peeling △(Yes): The peeled area is less than 80% of the surface ´(No): The peeled area is more than 80% of the surface

(外觀變化) 　　將與密著性之評價中使用者相同的試驗體，於60℃、相對濕度70%之條件下靜置3日。然後，藉由目視觀察一般加工品，依照以下所示的標準，評價有無外觀變化。「基準」　　○(良)：無外觀變化　　△(可)：白化的面積未達表面之80% 　　´(不行)：白化的面積為表面之80%以上(Appearance change) The same test body as the user in the evaluation of adhesion was left to stand for 3 days under the conditions of 60°C and 70% relative humidity. Then, general processed products were visually observed, and the presence or absence of changes in appearance was evaluated according to the criteria shown below. "Standard" ○ (Good): No change in appearance △ (Yes): The whitened area is less than 80% of the surface ´(No): The whitened area is more than 80% of the surface

如表11所示，實施例39～42之一般加工品係難燃性良好。又，實施例39～42之一般加工品係密著性及外觀變化之評價為「○(良)」或「△(可)」之評價。　　相對於其，比較例11之一般加工品由於塗料9不含來自(A)的構成成分，而難燃性不良。　　又，於實施例39～42之中，不使用磷系化合物的聚磷酸銨作為難燃劑的實施例39～41之一般加工品，係尤其密著性及外觀變化之評價良好。As shown in Table 11, the general processed strains of Examples 39 to 42 have good flame retardancy. In addition, the evaluation of the adhesiveness and the change in appearance of the general processed products of Examples 39 to 42 was the evaluation of "○ (good)" or "Δ (good)". On the other hand, the general processed product of Comparative Example 11 was poor in flame retardancy because the paint 9 did not contain the constituent components derived from (A). In addition, among Examples 39 to 42, the general processed products of Examples 39 to 41 in which ammonium polyphosphate without a phosphorus-based compound was used as a flame retardant were particularly good in evaluation of adhesion and appearance change.

「黏接著劑加工品」 (實施例43～45、比較例12) 　　以表12所示的比例，摻合藉由下述之方法所製造的丙烯酸樹脂(D)、表12所示的樹脂與交聯劑的季戊四醇聚環氧丙基醚(Nagase ChemteX股份有限公司製，Denacol EX411)，調製實施例43～45、比較例12所用之黏接著劑1～4。"Adhesive products" (Examples 43 to 45, Comparative Example 12) In the ratio shown in Table 12, the acrylic resin (D) produced by the following method, the resin shown in Table 12 and the Adhesives 1 to 4 used in Examples 43 to 45 and Comparative Example 12 were prepared using pentaerythritol polyglycidyl ether (Denacol EX411, manufactured by Nagase ChemteX Co., Ltd.) as a crosslinking agent.

表12所示的「樹脂1」表示實施例1之樹脂組成物，「樹脂3」表示實施例3之樹脂組成物，「樹脂5」表示實施例5之樹脂組成物，「樹脂28」表示比較例1之樹脂組成物。"Resin 1" shown in Table 12 represents the resin composition of Example 1, "Resin 3" represents the resin composition of Example 3, "Resin 5" represents the resin composition of Example 5, and "Resin 28" represents the comparison The resin composition of Example 1.

「丙烯酸樹脂(D)之製造」　　於附有攪拌機、溫度調節器、回流冷卻器、滴液漏斗、溫度計的反應裝置中，加入丙烯酸正丁酯150g、甲基丙烯酸甲酯34g、丙烯酸2-羥基乙酯2g與甲苯195g，於加熱回流開始後，添加聚合起始劑的偶氮雙異丁腈0.2g。於甲苯之回流溫度下使其反應8小時後，以甲苯稀釋，得到固體成分50質量%之丙烯酸樹脂(D)。"Manufacture of Acrylic Resin (D)" In a reaction apparatus equipped with a stirrer, a temperature controller, a reflux cooler, a dropping funnel, and a thermometer, 150 g of n-butyl acrylate, 34 g of methyl methacrylate, and 2-hydroxy acrylate were added. After 2 g of ethyl ester and 195 g of toluene, 0.2 g of azobisisobutyronitrile as a polymerization initiator was added after the heating under reflux was started. After making it react at the reflux temperature of toluene for 8 hours, it diluted with toluene, and obtained the acrylic resin (D) with a solid content of 50 mass %.

(實施例46) 　　以表12所示的比例，摻合藉由下述之方法所製造的丙烯酸樹脂(D)、表12所示的樹脂、難燃劑的聚磷酸銨(Clariant Chemicals股份有限公司製，Exolit AP422，磷原子含量32質量%)、交聯劑的季戊四醇聚環氧丙基醚(Nagase ChemteX股份有限公司製，Denacol EX411)，調製實施例46所用之黏接著劑5。(Example 46) In the ratio shown in Table 12, the acrylic resin (D) produced by the following method, the resin shown in Table 12, and the ammonium polyphosphate of flame retardant (Clariant Chemicals Co., Ltd.) were blended. Adhesive 5 used in Example 46 was prepared using Exolit AP422, phosphorus atom content: 32% by mass), and pentaerythritol polyglycidyl ether (Denacol EX411, manufactured by Nagase ChemteX Co., Ltd.) as a crosslinking agent.

使用如此般進行所得之黏接著劑1～5，以後述之方法製作實施例43～46、比較例12之黏接著劑加工品。Using the adhesive agents 1 to 5 obtained in this manner, the adhesive agent processed products of Examples 43 to 46 and Comparative Example 12 were produced by the method described later.

＜黏接著劑加工品之製作＞　　作為基材，準備厚度25μm之PET薄膜。然後，以乾燥後之厚度成為10μm之方式，將表12所示之黏接著劑1～5塗佈於基材，形成黏接著劑層。　　其後，於黏接著劑層上貼合剝離薄膜，以輥壓接，藉由在40℃熟化3日，得到黏接著劑加工品。<Preparation of processed adhesive product> As a base material, a PET film with a thickness of 25 μm was prepared. Then, the adhesive agent 1-5 shown in Table 12 was apply|coated to a base material so that the thickness after drying might become 10 micrometers, and the adhesive agent layer was formed. After that, a release film was attached to the adhesive layer, bonded with a roll, and aged at 40°C for 3 days to obtain an adhesive processed product.

然後，針對所得之黏接著劑加工品，藉由與紙加工品同樣之方法，求出相對於黏接著劑加工品之黏接著劑(處理劑)之固體成分量(質量%)。還有，作為「加工品之質量」，使用：將塗佈黏接著劑，貼合剝離薄膜，以輥壓接之基材，在經調整成內溫105℃±2℃的乾燥機內放置1小時而使其乾燥，於乾燥器內冷卻到室溫為止，以感度0.5mg以下的直讀天平所精秤之值。即，作為剝離薄膜亦包含於基材中者進行計算。表12中顯示其結果。Then, the solid content amount (mass %) of the adhesive agent (treatment agent) with respect to the adhesive agent processed product was calculated|required by the method similar to the paper processed product about the obtained adhesive agent processed product. In addition, as "quality of processed products", use: the substrates coated with adhesive agent, pasted with release films, and bonded with rolls are placed in a dryer adjusted to an internal temperature of 105°C ± 2°C for 1 After 1 hour, it was dried, cooled to room temperature in a desiccator, and the value was precisely weighed by a direct reading balance with a sensitivity of 0.5 mg or less. That is, it calculated as what was also included in a base material as a release film. The results are shown in Table 12.

針對實施例43～46、比較例12之黏接著劑加工品，藉由以下所示的評價方法，評價難燃性、初期黏著力、耐熱保持力。表12中顯示其結果。About the adhesive agent processed goods of Examples 43-46 and Comparative Example 12, flame retardance, initial stage adhesive force, and heat-resistant retention force were evaluated by the evaluation method shown below. The results are shown in Table 12.

(難燃性) 　　分別使用黏接著劑加工品中使用的黏接著劑1～5，與上述＜樹脂薄膜之作成＞同樣地製作薄膜，與使用樹脂組成物所作成的樹脂薄膜同樣地，評價黏接著劑加工品之難燃性。(Flammability) Using the adhesive agents 1 to 5 used in the adhesive agent processed product, respectively, a film was prepared in the same manner as in the above <Preparation of resin film>, and the adhesiveness was evaluated in the same manner as the resin film prepared using the resin composition. The flame retardancy of adhesive processed products.

(初期黏著力) 　　準備面積25mm´100mm的略矩形之黏接著劑加工品，剝離剝離薄膜而使黏接著劑層露出。於由SUS304所構成的不銹鋼研磨板上，使黏接著劑層側之面相向，載置黏接著劑加工品，於23℃、相對濕度50%之條件下使2kg輥來回1次，而在不銹鋼研磨板貼合黏接著劑加工品。在貼合後20分鐘後，依據JIS Z 0237：2000中規定的黏著力之測定方法，測定180度剝離強度(N/cm)，依照以下之基準進行評價。「基準」　　○(良)：2.0N/cm以上　　△(可)：1.5N/cm以上～未達2.0N/cm 　　´(不行)：未達1.5N/cm(Initial Adhesion) Prepare a roughly rectangular adhesive product with an area of 25mm×100mm, and peel off the release film to expose the adhesive layer. On a stainless steel lapping plate made of SUS304, the surface of the adhesive layer side is facing each other, and the adhesive product is placed, and a 2 kg roller is made to reciprocate once under the conditions of 23°C and 50% relative humidity. Grinding plate lamination adhesive processed product. 20 minutes after bonding, the 180-degree peel strength (N/cm) was measured in accordance with the method for measuring the adhesive force specified in JIS Z 0237:2000, and evaluated according to the following criteria. "Standard" ○(Good): 2.0N/cm or more △(Fair): 1.5N/cm or more to less than 2.0N/cm ´(No): less than 1.5N/cm

(耐熱保持力) 　　除了設為使貼合面積成為25mm´25mm之略正方形以外，與測定初期黏著力時同樣地，在不銹鋼研磨板貼合黏接著劑加工品。然後，依據JIS Z 0237中規定的保持力之測定方法，施加1kg的荷重，測定1小時以上不落下的溫度之上限值，依照以下之基準進行評價。「基準」　　○(良)：150℃以上　　△(可)：100℃以上～未達150℃ 　　´(不行)：未達100℃(Heat Resistant Retention) The adhesive product was attached to the stainless steel grinding plate in the same manner as in the measurement of the initial adhesion, except that the lamination area was made into a roughly square shape of 25mm x 25mm. Then, according to the method for measuring the holding force specified in JIS Z 0237, a load of 1 kg was applied, and the upper limit of the temperature that did not drop for 1 hour or more was measured, and the evaluation was performed according to the following criteria. "Standard" ○ (good): 150°C or more △ (ok): 100°C or more to less than 150°C ´ (not possible): less than 100°C

如表12所示，實施例43～46之黏接著劑加工品皆為「○(良)」或「△(可)」之評價，難燃性、初期黏著力、耐熱保持力為良好。　　相對於其，比較例12之黏接著劑加工品由於黏接著劑4不含來自(A)的構成成分，而難燃性不良。　　又，於實施例43～46之中，不使用磷系化合物的聚磷酸銨作為難燃劑的實施例43～45之黏接著劑加工品，係尤其初期密著力及耐熱保持力之評價良好。 [產業上的利用可能性]As shown in Table 12, the processed adhesive products of Examples 43 to 46 were all evaluated as "○ (good)" or "Δ (good)", and the flame retardancy, initial adhesion, and heat retention were good. On the other hand, since the adhesive agent 4 of the comparative example 12 does not contain the constituent component derived from (A), it is inferior in flame retardancy. In addition, among Examples 43 to 46, the processed adhesive products of Examples 43 to 45 in which ammonium polyphosphate of no phosphorus-based compound was used as the flame retardant were particularly good in the evaluation of initial adhesion and heat resistance. [Industrial availability]

本發明提供一種樹脂，其係難燃性優異，抗滲出性及抗黏連性良好。　　本發明之共聚物係難燃性優異，在作為加工品的材料使用時，可得到抗滲出性及抗黏連性良好之加工品。因此，包含本發明之共聚物的處理劑係適合作為紙處理劑、纖維處理劑、一般塗料、接著劑及黏著劑。The present invention provides a resin which is excellent in flame retardancy and good in bleed resistance and blocking resistance. The copolymer of the present invention is excellent in flame retardancy, and when used as a material for a processed product, a processed product with good bleed resistance and blocking resistance can be obtained. Therefore, the treatment agent containing the copolymer of the present invention is suitable as a paper treatment agent, a fiber treatment agent, a general paint, an adhesive, and an adhesive.

包含本發明之共聚物的處理劑係適合作為難燃性、抗滲出性、抗黏連性、硬挺性優異之加工品的材料。例如，作為基材是紙的加工品，可舉出壁紙、壁紙用襯底紙等之建築材料、汽車內部裝飾材料等。又，作為基材是纖維的加工品，可舉出窗簾等的內部裝飾材料、電子材料用緩衝材、家電用緩衝材、汽車內裝緩衝材、汽車椅墊等。The treatment agent containing the copolymer of the present invention is suitable as a material for a processed product excellent in flame retardancy, bleed resistance, blocking resistance, and stiffness. For example, as a processed product of paper as a base material, building materials, such as a wallpaper and backing paper for wallpaper, an automobile interior material, etc. are mentioned. Moreover, as a processed product which a base material is a fiber, interior materials, such as a curtain, a cushion material for electronic materials, a cushion material for household appliances, an automobile interior cushion material, a car seat cushion, etc. are mentioned.

又，包含本發明之共聚物的塗料及黏接著劑，係可適用於製造一般加工品、黏接著劑加工品等的加工品之際。作為此等之加工品，例如可舉出接著膠帶、家電、電子零件、黏著膠帶、雙面膠帶、黏著標籤等之日用品、壁紙、地磚、地墊(緩衝地板)、地毯、天花板材料、窗用黏著片等之住宅用材料、汽車用製品、家電製品、電子零件等。Moreover, the coating material and the adhesive agent containing the copolymer of this invention can be used suitably when manufacturing processed goods, such as a general processed product and an adhesive agent processed product. Examples of such processed products include adhesive tapes, household appliances, electronic parts, adhesive tapes, double-sided tapes, adhesive labels, and other daily necessities, wallpapers, floor tiles, floor mats (buffer floors), carpets, ceiling materials, and windows. Household materials such as adhesive sheets, automotive products, home appliances, electronic parts, etc.

Claims

一種紙處理劑，其係包含具有來自含磷不飽和單體(A)的構成成分與來自聚合性不飽和單體(B)的構成成分之共聚物之紙處理劑，其特徵為：前述來自聚合性不飽和單體(B)的構成成分包含來自具有碳原子數及氧原子數之合計為4~10的主鏈之不飽和羧酸單體(b-1)的構成成分，且前述共聚物中，相對於前述來自含磷不飽和單體(A)的構成成分與前述來自聚合性不飽和單體(B)的構成成分之合計含量，來自具有碳數為1~4的烷基之(甲基)丙烯酸烷酯單體(b-2)的構成成分之含量為0.00~1.00質量%，前述來自含磷不飽和單體(A)的構成成分係包含來自具有式(1)所示的磷酸基與式(2)所示的亞磷酸基的任一者之單體(a-1)的構成成分，

(式(1)中，＊表示與構成不飽和單體的原子之鍵結部)

(式(2)中，＊表示與構成不飽和單體的原子之鍵結部)，前述共聚物之酸價為300~800mgKOH/g。 A paper treating agent comprising a copolymer having a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B), characterized in that the aforementioned constituents derived from The constituents of the polymerizable unsaturated monomer (B) include constituents derived from the unsaturated carboxylic acid monomer (b-1) having a main chain having a total number of carbon atoms and oxygen atoms of 4 to 10, and the aforementioned copolymerization Among them, with respect to the total content of the aforementioned constituent components derived from the phosphorus-containing unsaturated monomer (A) and the aforementioned constituent components derived from the polymerizable unsaturated monomer (B), it is derived from the ratio of the alkyl group having 1 to 4 carbon atoms. The content of the constituent components of the alkyl (meth)acrylate monomer (b-2) is 0.00 to 1.00 mass %, and the constituent components derived from the phosphorus-containing unsaturated monomer (A) are derived from the components represented by the formula (1). The constituents of the monomer (a-1) of either the phosphoric acid group represented by the formula (2) or the phosphorous acid group represented by the formula (2),

(In formula (1), * represents a bond with an atom constituting an unsaturated monomer)

(In the formula (2), * represents a bond with an atom constituting an unsaturated monomer.) The acid value of the copolymer is 300 to 800 mgKOH/g.

如請求項1之紙處理劑，其中前述具有磷酸基與亞磷酸基的任一者之單體(a-1)為酸性‧膦醯氧基聚氧化烯二醇單(甲基)丙烯酸酯。 The paper treating agent of claim 1, wherein the aforementioned has a phosphoric acid group and phosphorous The monomer (a-1) of any one of the acid groups is acid phosphonooxypolyoxyalkylene glycol mono(meth)acrylate.

如請求項1或2之紙處理劑，其中，前述共聚物中之磷原子含量為0.1~10質量%。 The paper treating agent according to claim 1 or 2, wherein the content of phosphorus atoms in the copolymer is 0.1 to 10% by mass.

如請求項1之紙處理劑，其中前述不飽和羧酸單體(b-1)係由丙烯酸、甲基丙烯酸、伊康酸、β-羧基乙基丙烯酸所選出的至少1種。 The paper treating agent according to claim 1, wherein the unsaturated carboxylic acid monomer (b-1) is at least one selected from acrylic acid, methacrylic acid, itaconic acid, and β-carboxyethyl acrylic acid.

如請求項1之紙處理劑，其中，前述共聚物中，相對於前述來自含磷不飽和單體(A)的構成成分與前述來自聚合性不飽和單體(B)的構成成分之合計含量，前述來自不飽和羧酸單體(b-1)的構成成分之含量為30~95質量%。 The paper treating agent according to claim 1, wherein in the copolymer, the total content of the constituents derived from the phosphorus-containing unsaturated monomer (A) and the constituents derived from the polymerizable unsaturated monomer (B) is , the content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) is 30 to 95% by mass.

如請求項1之紙處理劑，其進一步包含來自鏈轉移劑(C)的構成成分。 The paper treating agent according to claim 1, which further contains a structural component derived from a chain transfer agent (C).

如請求項6之紙處理劑，其中前述鏈轉移劑(C)為巰基烷基羧酸酯(c-1)。 The paper treating agent according to claim 6, wherein the chain transfer agent (C) is a mercapto alkyl carboxylate (c-1).

如請求項6或7之紙處理劑，其中，前述共聚物中，相對於前述來自含磷不飽和單體(A)的構成成分與前述來自聚合性不飽和單體(B)的構成成分之合計含量100質量份，前述來自鏈轉移劑(C)的構成成分之含量為0.1~10質量份。 The paper treating agent according to claim 6 or 7, wherein, in the copolymer, with respect to the difference between the constituent component derived from the phosphorus-containing unsaturated monomer (A) and the constituent component derived from the polymerizable unsaturated monomer (B) The total content is 100 parts by mass, The content of the constituent components derived from the chain transfer agent (C) is 0.1 to 10 parts by mass.

如請求項1之紙處理劑，其中，前述共聚物之質量平均分子量為25000~70000。 The paper treating agent according to claim 1, wherein the mass-average molecular weight of the copolymer is 25,000 to 70,000.

一種纖維處理劑，其係包含具有來自含磷不飽和單體(A)的構成成分與來自聚合性不飽和單體(B)的構成成分之共聚物之纖維處理劑，其特徵為：前述來自聚合性不飽和單體(B)的構成成分包含來自具有碳原子數及氧原子數之合計為4~10的主鏈之不飽和羧酸單體(b-1)的構成成分，且前述共聚物中，相對於前述來自含磷不飽和單體(A)的構成成分與前述來自聚合性不飽和單體(B)的構成成分之合計含量，來自具有碳數為1~4的烷基之(甲基)丙烯酸烷酯單體(b-2)的構成成分之含量為0.00~1.00質量%，前述來自含磷不飽和單體(A)的構成成分係包含來自具有式(1)所示的磷酸基與式(2)所示的亞磷酸基的任一者之單體(a-1)的構成成分，

(式(1)中，＊表示與構成不飽和單體的原子之鍵結部)

(式(2)中，＊表示與構成不飽和單體的原子之鍵結部)，前述共聚物之酸價為300~800mgKOH/g。 A fiber treatment agent comprising a copolymer having a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B), characterized in that the aforementioned constituents derived from The constituents of the polymerizable unsaturated monomer (B) include constituents derived from the unsaturated carboxylic acid monomer (b-1) having a main chain having a total number of carbon atoms and oxygen atoms of 4 to 10, and the aforementioned copolymerization Among them, with respect to the total content of the aforementioned constituent components derived from the phosphorus-containing unsaturated monomer (A) and the aforementioned constituent components derived from the polymerizable unsaturated monomer (B), it is derived from the ratio of the alkyl group having 1 to 4 carbon atoms. The content of the constituent components of the alkyl (meth)acrylate monomer (b-2) is 0.00 to 1.00 mass %, and the constituent components derived from the phosphorus-containing unsaturated monomer (A) are derived from the components represented by the formula (1). The constituents of the monomer (a-1) of either the phosphoric acid group represented by the formula (2) or the phosphorous acid group represented by the formula (2),

如請求項10之纖維處理劑，其中前述具有磷酸基與亞磷酸基的任一者之單體(a-1)為酸性‧膦醯氧基聚氧化烯二醇單(甲基)丙烯酸酯。 The fiber treatment agent according to claim 10, wherein the monomer (a-1) having either a phosphoric acid group or a phosphorous acid group is an acid phosphonooxypolyoxyalkylene glycol mono(meth)acrylate.

如請求項10或11之纖維處理劑，其中，前述共聚物中之磷原子含量為0.1~10質量%。 The fiber treatment agent according to claim 10 or 11, wherein the content of phosphorus atoms in the copolymer is 0.1 to 10% by mass.

如請求項10之纖維處理劑，其中前述不飽和羧酸單體(b-1)係由丙烯酸、甲基丙烯酸、伊康酸、β-羧基乙基丙烯酸所選出的至少1種。 The fiber treating agent according to claim 10, wherein the unsaturated carboxylic acid monomer (b-1) is at least one selected from acrylic acid, methacrylic acid, itaconic acid, and β-carboxyethyl acrylic acid.

如請求項10之纖維處理劑，其中，前述共聚物中，相對於前述來自含磷不飽和單體(A)的構成成分與前述來自聚合性不飽和單體(B)的構成成分之合計含量，前述來自不飽和羧酸單體(b-1)的構成成分之含量為30~95質量%。 The fiber treating agent according to claim 10, wherein in the copolymer, the total content of the constituents derived from the phosphorus-containing unsaturated monomer (A) and the constituents derived from the polymerizable unsaturated monomer (B) is , the content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) is 30 to 95% by mass.

如請求項10之纖維處理劑，其進一步包含來自鏈轉移劑(C)的構成成分。 The fiber-treating agent of Claim 10 which further contains the structural component derived from a chain transfer agent (C).

如請求項15之纖維處理劑，其中前述鏈轉移劑(C)為巰基烷基羧酸酯(c-1)。 The fiber treatment agent according to claim 15, wherein the chain transfer agent (C) is a mercapto alkyl carboxylate (c-1).

如請求項15或16之纖維處理劑，其中，前述共聚物中，相對於前述來自含磷不飽和單體(A)的構成成分與前述來自聚合性不飽和單體(B)的構成成分之合計含量100質量份，前述來自鏈轉移劑(C)的構成成分之含量為0.1~10質量份。 The fiber-treating agent according to claim 15 or 16, wherein, in the copolymer, the ratio of the constituent component derived from the phosphorus-containing unsaturated monomer (A) to the constituent component derived from the polymerizable unsaturated monomer (B) The total content is 100 parts by mass, and the content of the constituent components derived from the chain transfer agent (C) is 0.1 to 10 parts by mass.

如請求項10之纖維處理劑，其中，前述共聚物之質量平均分子量為25000~70000。 The fiber treatment agent according to claim 10, wherein the mass-average molecular weight of the copolymer is 25,000 to 70,000.

一種紙加工品，其係共聚物附著於紙上之紙加工品，該共聚物係具有來自含磷不飽和單體(A)的構成成分，及來自聚合性不飽和單體(B)的構成成分，及來自鏈轉移劑(C)的構成成分，其中，前述來自聚合性不飽和單體(B)的構成成分係包含來自具有碳原子數及氧原子數之合計為4~10的主鏈之不飽和羧酸單體(b-1)的構成成分，且前述共聚物中，相對於前述來自含磷不飽和單體(A)的構成成分與前述來自聚合性不飽和單體(B)的構成成分之合計含量，來自具有碳數為1~4的烷基之(甲基)丙烯酸烷酯單體(b-2)的構成成分之含量為0.00~1.00質量%，且，前述來自含磷不飽和單體(A)的構成成分係包含來自具有式(1)所示的磷酸基與式(2)所示的亞磷酸基的任一者之單體(a-1)的構成成分，

(式(1)中，＊表示與構成不飽和單體的原子之鍵結部)

(式(2)中，＊表示與構成不飽和單體的原子之鍵結部)前述共聚物之酸價為300~800mgKOH/g，且相對於前述紙100質量份，係包含前述共聚物1~70質量份。 A paper processed product in which a copolymer is attached to paper, the copolymer having a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B) , and the constituents derived from the chain transfer agent (C), wherein the aforementioned constituents derived from the polymerizable unsaturated monomer (B) include those derived from the main chain having a total of 4 to 10 carbon atoms and oxygen atoms. The constituent component of the unsaturated carboxylic acid monomer (b-1), and in the copolymer, the constituent component derived from the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B)-derived component The total content of the constituent components is 0.00 to 1.00 mass %, and the content of the constituent components derived from the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms is 0.00 to 1.00 mass %. The constituent component of the unsaturated monomer (A) is a constituent component derived from the monomer (a-1) having either a phosphoric acid group represented by the formula (1) or a phosphorous acid group represented by the formula (2),

(In the formula (2), * represents a bond with an atom constituting an unsaturated monomer) The acid value of the copolymer is 300 to 800 mgKOH/g, and the copolymer 1 is included with respect to 100 parts by mass of the paper. ~70 parts by mass.

一種纖維加工品，其係共聚物附著於纖維加工品上之纖維加工品，該共聚物係具有來自含磷不飽和單體(A)的構成成分，及來自聚合性不飽和單體(B)的構成成分，及來自鏈轉移劑(C)的構成成分，其中，前述來自聚合性不飽和單體(B)的構成成分係包含來自具有碳原子數及氧原子數之合計為4~10的主鏈之不飽和羧酸單體(b-1)的構成成分，且前述共聚物中，相對於前述來自含磷不飽和單體(A)的構成成分與前述來自聚合性不飽和單體(B)的構成成分之合計含量，來自具有碳數為1~4的烷基之(甲基)丙烯酸烷酯單體(b-2)的構成成分之含量為0.00~1.00質量%，且，前述來自含磷不飽和單體(A)的構成成分係包含來自具有式(1)所示的磷酸基與式(2)所示的亞磷酸基的任一者之單體(a-1)的構成成分，

(式(1)中，＊表示與構成不飽和單體的原子之鍵結部)

(式(2)中，＊表示與構成不飽和單體的原子之鍵結部)，前述共聚物之酸價為300~800mgKOH/g，且相對於前述纖維100質量份，係包含前述共聚物1~70質量份。 A fiber processed product comprising a fiber processed product in which a copolymer is adhered to the fiber processed product, the copolymer having a constituent derived from a phosphorus-containing unsaturated monomer (A), and a polymer derived from a polymerizable unsaturated monomer (B) The constituents of , and the constituents derived from the chain transfer agent (C), wherein the constituents derived from the polymerizable unsaturated monomer (B) are derived from those having a total of 4 to 10 carbon atoms and oxygen atoms. The constituent component of the unsaturated carboxylic acid monomer (b-1) in the main chain, and in the copolymer, with respect to the constituent component derived from the phosphorus-containing unsaturated monomer (A) and the aforementioned polymerizable unsaturated monomer ( The total content of the constituent components of B), the content of the constituent components derived from the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms is 0.00 to 1.00 mass %, and the aforementioned The constituent component derived from the phosphorus-containing unsaturated monomer (A) contains the monomer (a-1) derived from either the phosphoric acid group represented by the formula (1) and the phosphorous acid group represented by the formula (2). constituents,

(In formula (2), * represents a bond with an atom constituting an unsaturated monomer), the acid value of the copolymer is 300 to 800 mgKOH/g, and the copolymer is contained in 100 parts by mass of the fiber. 1 to 70 parts by mass.