TWI754078B - Radical polymerizable resin composition and structural repair material - Google Patents

Radical polymerizable resin composition and structural repair material Download PDF

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TWI754078B
TWI754078B TW107121788A TW107121788A TWI754078B TW I754078 B TWI754078 B TW I754078B TW 107121788 A TW107121788 A TW 107121788A TW 107121788 A TW107121788 A TW 107121788A TW I754078 B TWI754078 B TW I754078B
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radically polymerizable
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polymerizable resin
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TW201906952A (en
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小林健一
亀山絵梨
黒木一博
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日商昭和電工股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
    • E04G23/00—Working measures on existing buildings
    • E04G23/02—Repairing, e.g. filling cracks; Restoring; Altering; Enlarging

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Abstract

本發明提供具有低溫硬化性，展現優良之接著強度的自由基聚合性樹脂組成物、使用該自由基聚合性樹脂組成物之構造物修復材料。 　　本發明為以含有(A)自由基聚合性樹脂、(B)自由基聚合性不飽和單體、(C)胺系硬化促進劑與(D)多官能硫醇化合物為特徵之自由基聚合性樹脂組成物及使用其而成之構造物修復材料。The present invention provides a radically polymerizable resin composition having low-temperature curability and exhibiting excellent adhesive strength, and a structural repair material using the radically polymerizable resin composition. The present invention is a radically polymerizable resin characterized by containing (A) a radically polymerizable resin, (B) a radically polymerizable unsaturated monomer, (C) an amine-based curing accelerator, and (D) a polyfunctional thiol compound. Resin composition and structural repair material using the same.

Description

自由基聚合性樹脂組成物及構造物修復材料Radical polymerizable resin composition and structural repair material

本發明係關於滿足低溫硬化性與接著強度之兩物性的自由基聚合性樹脂組成物。進一步地，係關於含有適於修復因混凝土構造物之劣化等所產生的龜裂之前述自由基聚合性樹脂組成物的構造物修復材料。The present invention relates to a radically polymerizable resin composition satisfying both physical properties of low-temperature curability and adhesive strength. Furthermore, it relates to a structure repairing material containing the above-mentioned radically polymerizable resin composition suitable for repairing cracks caused by deterioration of a concrete structure or the like.

自以往，作為混凝土構造物之經年劣化等的補修/補強材料，係提出有使用環氧樹脂或丙烯酸樹脂漿等之合成樹脂的方法，作為課題之一，列舉有冬季之施工等低溫硬化性的改善。 　　(專利文獻1~3)。 　　又，對於如高速公路或鐵道等之高欄壁般，經常伴隨振動的混凝土構造物，為了不產生補修材之固著、乾燥後的斷裂，課題係列舉有硬化物之裂痕隨附性等。對如此之課題，例如專利文獻4中已知使用丙烯酸/苯乙烯樹脂作為混合劑之混凝土構造物的補修/補強劑，專利文獻5中已知使用丙烯酸系樹脂等之玻璃轉移溫度為-25℃以下的聚合物。 　　(專利文獻4~5)。 [先前技術文獻] [專利文獻]Conventionally, a method of using a synthetic resin such as epoxy resin or acrylic resin paste has been proposed as a repair/reinforcing material for the deterioration of concrete structures over time, etc. As one of the problems, low temperature hardening properties such as construction in winter are mentioned. improvement. (Patent Documents 1 to 3). In addition, for concrete structures such as highways and railways, which are often vibrated, in order not to cause fixing of repair materials and cracks after drying, the series of issues include the attachment of cracks to hardened materials. For such a problem, for example, a repair/reinforcing agent for concrete structures using an acrylic/styrene resin as a mixture is known in Patent Document 4, and a glass transition temperature of -25°C is known in Patent Document 5 using an acrylic resin or the like. the following polymers. (Patent Documents 4~5). [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開2003-002948號公報 　　[專利文獻2]日本特開2001-247636號公報 　　[專利文獻3]日本特開2000-154297號公報 　　[專利文獻4]日本特開2009-019354號公報 　　[專利文獻5]日本特開2012-091985號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 2003-002948 [Patent Document 2] Japanese Patent Application Laid-Open No. 2001-247636 [Patent Document 3] Japanese Patent Application Laid-Open No. 2000-154297 [Patent Document 4] Japanese Patent Application Laid-Open No. 2009-019354 No. [Patent Document 5] Japanese Patent Application Laid-Open No. 2012-091985

[發明所欲解決之課題][The problem to be solved by the invention]

但是，上述記載之專利文獻1~5記載的方法，對於經常伴隨振動之混凝土構造物，接著強度亦不充分，用於進行龜裂部分之修復係有改善的餘地。 　　本發明係有鑑於上述以往之實情而為者，其目的為提供具有低溫硬化性，展現優良之接著強度的自由基聚合性樹脂組成物、使用該自由基聚合性樹脂組成物之構造物修復材料。 [用以解決課題之手段]However, the methods described in Patent Documents 1 to 5 described above have insufficient adhesive strength for concrete structures that are often vibrated, and there is room for improvement for repairing cracked parts. The present invention is made in view of the above-mentioned conventional circumstances, and its object is to provide a radically polymerizable resin composition having low-temperature curability and exhibiting excellent adhesive strength, and a structural repair material using the radically polymerizable resin composition . [means to solve the problem]

亦即，本發明以下述[1]~[18]為要旨。 　　[1]一種自由基聚合性樹脂組成物，其特徵為含有(A)自由基聚合性樹脂、(B)自由基聚合性不飽和單體、(C)胺系硬化促進劑與(D)多官能硫醇化合物。 　　[2]如上述[1]之自由基聚合性樹脂組成物，其中前述(A)成分，為選自乙烯酯樹脂、不飽和聚酯樹脂、聚酯(甲基)丙烯酸酯樹脂、胺基甲酸酯(甲基)丙烯酸酯樹脂的至少1種。 　　[3]如上述[1]或[2]之自由基聚合性樹脂組成物，其中前述(D)成分，為具有下述式(Q)表示之構造的化合物；

Figure 02_image001
(通式(Q)中，R1 及R2 ，係分別獨立地為氫原子、碳數1~10之烷基或碳數6~18之芳香族基；*表示係連結於具有至少1個巰基之任意有機基；a為0~2之整數)。 　　[4]如上述[1]~[3]中任一項之自由基聚合性樹脂組成物，其中前述(D)成分，為具有下述通式(Q-1)表示之構造的化合物；
Figure 02_image003
(通式(Q-1)中，R1 及R2 ，係分別獨立地為氫原子、碳數1~10之烷基或碳數6~18之芳香族基；**表示係連結於具有至少1個巰基之任意有機基；a為0~2之整數)。 　　[5]如上述[1]~[4]中任一項之自由基聚合性樹脂組成物，其中前述(D)成分，為選自2~6官能之多官能硫醇化合物的至少1種。 　　[6]如上述[1]~[5]中任一項之自由基聚合性樹脂組成物，其中以前述(A)成分與前述(B)成分之合計量為100質量份時，前述(A)成分之含量為5~95質量份、前述(B)成分之含量為5~95質量份、前述成分(C)之含量為0.01~10質量份、前述成分(D)之含量為0.1~20質量份。 　　[7]如上述[1]~[6]中任一項之自由基聚合性樹脂組成物，其中前述(C)成分，含有選自由N,N-二甲基苯胺、N,N-二甲基-p-甲苯胺、N,N-雙(2-羥基乙基)-p-甲苯胺、N,N-雙(2-羥基丙基)-p-甲苯胺、N,N-雙(2-羥基乙基)苯胺所成之群的至少1種。 　　[8]如上述[1]~[7]中任一項之自由基聚合性樹脂組成物，其進一步含有金屬有機化合物，作為胺系硬化促進劑以外之硬化促進劑。 　　[9]如上述[8]之自由基聚合性樹脂組成物，其中以前述(A)成分與前述(B)成分之合計量為100質量份時，前述金屬有機化合物之含量為0.1~5質量份。 　　[10]如上述[8]或[9]之自由基聚合性樹脂組成物，其中前述金屬有機化合物，含有選自由鈷化合物、銅化合物所成之群的至少1種。 　　[11]如上述[1]~[10]中任一項之自由基聚合性樹脂組成物，其進一步含有(E)硬化劑。 　　[12]如上述[11]之自由基聚合性樹脂組成物，其中以前述(A)成分與前述(B)成分之合計量為100質量份時，前述(E)成分之含量為0.1~10質量份。 　　[13]如上述[11]或[12]之自由基聚合性樹脂組成物，其中前述(E)成分，含有選自由二苯甲醯基過氧化物、苯甲醯基m-甲基苯甲醯基過氧化物、m-甲苯甲醯基過氧化物、甲基乙基酮過氧化物、異丙苯氫過氧化物、過氧苯甲酸t-丁酯所成之群的至少1種。 　　[14]一種構造物修復材料，其含有如上述[1]~[13]中任一項之自由基聚合性樹脂組成物。 　　[15]一種構造物修復材料，其含有如上述[1]~[13]中任一項之自由基聚合性樹脂組成物及(F)填充材料。 　　[16]如上述[15]之構造物修復材料，其中以前述(A)成分與前述(B)成分之合計量為100質量份時，前述(F)成分之含量為1~700質量份。 　　[17]如上述[15]或[16]之構造物修復材料，其中前述(F)成分，為選自由矽砂、碳酸鈣、滑石及發煙二氧化矽所成之群的至少1種。 　　[18]如上述[14]~[17]中任一項之構造物修復材料，其中前述構造物修復材料，為版式軌道之構造物修復材料。 [發明之效果]That is, the gist of the present invention is based on the following [1] to [18]. [1] A radically polymerizable resin composition comprising (A) a radically polymerizable resin, (B) a radically polymerizable unsaturated monomer, (C) an amine-based curing accelerator, and (D) a poly Functional thiol compounds. [2] The radically polymerizable resin composition according to the above [1], wherein the component (A) is selected from the group consisting of vinyl ester resins, unsaturated polyester resins, polyester (meth)acrylate resins, and urethane resins. At least one type of acid ester (meth)acrylate resin. [3] The radically polymerizable resin composition according to the above [1] or [2], wherein the component (D) is a compound having a structure represented by the following formula (Q);
Figure 02_image001
(In the general formula (Q), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms; Any organic group of mercapto group; a is an integer of 0~2). [4] The radically polymerizable resin composition according to any one of the above [1] to [3], wherein the component (D) is a compound having a structure represented by the following general formula (Q-1);
Figure 02_image003
(In the general formula (Q-1), R 1 and R 2 are independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms; Any organic group with at least one mercapto group; a is an integer from 0 to 2). [5] The radically polymerizable resin composition according to any one of the above [1] to [4], wherein the component (D) is at least one selected from the group consisting of 2- to 6-functional polyfunctional thiol compounds. [6] The radically polymerizable resin composition according to any one of the above [1] to [5], wherein when the total amount of the above-mentioned (A) component and the above-mentioned (B) component is 100 parts by mass, the above-mentioned (A) ) The content of the component is 5 to 95 parts by mass, the content of the component (B) is 5 to 95 parts by mass, the content of the component (C) is 0.01 to 10 parts by mass, and the content of the component (D) is 0.1 to 20 parts by mass parts by mass. [7] The radically polymerizable resin composition according to any one of the above [1] to [6], wherein the component (C) contains a component selected from the group consisting of N,N-dimethylaniline, N,N-dimethylaniline yl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxypropyl)-p-toluidine, N,N-bis(2 -At least one of the group consisting of hydroxyethyl)aniline. [8] The radically polymerizable resin composition according to any one of the above [1] to [7], which further contains a metal organic compound as a curing accelerator other than the amine-based curing accelerator. [9] The radically polymerizable resin composition according to the above [8], wherein the content of the metal organic compound is 0.1 to 5 mass parts when the total amount of the aforementioned (A) component and the aforementioned (B) component is 100 parts by mass share. [10] The radically polymerizable resin composition according to the above [8] or [9], wherein the metal organic compound contains at least one selected from the group consisting of cobalt compounds and copper compounds. [11] The radically polymerizable resin composition according to any one of the above [1] to [10], which further contains (E) a curing agent. [12] The radical polymerizable resin composition according to the above [11], wherein the content of the component (E) is 0.1 to 10 when the total amount of the component (A) and the component (B) is 100 parts by mass. parts by mass. [13] The radically polymerizable resin composition according to the above [11] or [12], wherein the component (E) contains a compound selected from the group consisting of dibenzoyl peroxide, benzyl m-methylbenzyl At least one of the group consisting of acyl peroxide, m-tolyl acyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, and t-butyl peroxybenzoate. [14] A structure repair material comprising the radically polymerizable resin composition according to any one of the above [1] to [13]. [15] A structure repair material comprising the radically polymerizable resin composition according to any one of the above [1] to [13] and (F) a filler. [16] The structural repair material according to the above [15], wherein the content of the component (F) is 1 to 700 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass. [17] The structural repair material according to the above [15] or [16], wherein the component (F) is at least one selected from the group consisting of silica sand, calcium carbonate, talc, and fumed silica. [18] The structure repair material according to any one of the above [14] to [17], wherein the structure repair material is a structure repair material of a layout track. [Effect of invention]

依照本發明，可提供具有低溫硬化性，且展現優良之接著強度的自由基聚合性樹脂組成物。含有具有如此特性之自由基聚合性組成物的構造物修復材料，具有低溫硬化性，因此於低溫環境下亦可快速硬化，且具有優良之接著強度，故於快速硬化且收縮率大的場合，亦不易產生固著/乾燥後之斷裂或修復部位與修復材料界面之剝離。使用本發明之構造物修復材料時，對經常伴隨振動之混凝土構造物，可良好地進行龜裂部分之修復。亦即，可提供固著時可展現優良之附著強度，且不產生固著後之斷裂等的構造物修復材料。According to the present invention, it is possible to provide a radically polymerizable resin composition having low-temperature curability and exhibiting excellent adhesive strength. The structural repair material containing the radically polymerizable composition with such characteristics has low temperature curability, so it can be cured rapidly in a low temperature environment, and has excellent adhesive strength, so in the case of rapid curing and large shrinkage, It is also not easy to produce cracks after fixing/drying or peeling of the interface between the repaired part and the repairing material. When the structure repairing material of the present invention is used, the repair of the cracked part can be carried out favorably for the concrete structure which is often accompanied by vibration. That is, it is possible to provide a structure repairing material that exhibits excellent adhesion strength during fixation and does not cause breakage after fixation.

[自由基聚合性樹脂組成物] 　　本發明之自由基聚合性樹脂組成物，係以含有(A)自由基聚合性樹脂、(B)自由基聚合性不飽和單體、(C)胺系硬化促進劑與(D)多官能硫醇化合物為特徵的自由基聚合性樹脂組成物。 　　再者，有將(A)自由基聚合性樹脂稱為(A)成分者、有將(B)自由基聚合性不飽和單體稱為(B)成分者、有將(C)胺系硬化促進劑稱為(C)成分者、有將(D)多官能硫醇化合物稱為(D)成分者。[Radical Polymerizable Resin Composition] The radically polymerizable resin composition of the present invention contains (A) a radically polymerizable resin, (B) a radically polymerizable unsaturated monomer, and (C) an amine-based curing agent. A radical polymerizable resin composition characterized by an accelerator and a (D) polyfunctional thiol compound. In addition, (A) radical polymerizable resin is called (A) component, (B) radical polymerizable unsaturated monomer is called (B) component, (C) amine type hardening is called The accelerator is referred to as (C) component, and the (D) polyfunctional thiol compound is referred to as (D) component.

＜自由基聚合性樹脂(A)＞ 　　本發明中，自由基聚合性樹脂(A)，係指於樹脂中具有乙烯性不飽和基，藉由自由基而進行聚合反應之化合物。 　　自由基聚合性樹脂(A)，可列舉胺基甲酸酯(甲基)丙烯酸酯樹脂、乙烯酯樹脂、不飽和聚酯樹脂、聚酯(甲基)丙烯酸酯樹脂、(甲基)丙烯酸酯樹脂等，其中就自由基聚合性樹脂組成物之硬化物的柔軟性之觀點而言，尤以胺基甲酸酯(甲基)丙烯酸酯樹脂或具有韌性之乙烯酯樹脂為佳。再者，本說明書中，「(甲基)丙烯酸酯」，意指「丙烯酸酯或甲基丙烯酸酯」。<Radical polymerizable resin (A)> In the present invention, the radical polymerizable resin (A) refers to a compound which has an ethylenically unsaturated group in the resin and undergoes a radical polymerization reaction. The radical polymerizable resin (A) includes urethane (meth)acrylate resin, vinyl ester resin, unsaturated polyester resin, polyester (meth)acrylate resin, and (meth)acrylate Among resins, etc., from the viewpoint of the flexibility of the cured product of the radically polymerizable resin composition, a urethane (meth)acrylate resin or a tough vinyl ester resin is particularly preferable. In addition, in this specification, "(meth)acrylate" means "acrylate or methacrylate".

[胺基甲酸酯(甲基)丙烯酸酯樹脂] 　　胺基甲酸酯(甲基)丙烯酸酯樹脂，例如可使用對使多元異氰酸酯與多元醇反應而得的聚胺基甲酸酯之兩末端的羥基或異氰酸基導入(甲基)丙烯醯基而得之樹脂。 　　多元醇可無特別限制地使用作為日本特開2009-292890號公報、WO2016/171151號公報記載之「聚羥基化合物」或「多元醇類」所記載的化合物。 　　多元醇並無特別限制，例如，可列舉聚酯多元醇、聚醚多元醇； 　　乙二醇、丙二醇、二乙二醇、二丙二醇、環己烷二甲醇等之2元醇； 　　以氫化或非氫化雙酚A等為代表的2元醇與以環氧丙烷或環氧乙烷為代表的環氧烷之加成物等之2元醇； 　　1,2,3,4-四羥基丁烷、甘油、三羥甲基丙烷、季戊四醇等之3元以上之醇等。 　　上述2元醇與環氧烷之加成物，例如可列舉聚氧化烯雙酚A醚。 　　此等之中，胺基甲酸酯(甲基)丙烯酸酯樹脂，尤以包含由聚酯多元醇、聚醚多元醇、聚氧化烯雙酚A醚中選出的多元醇構造之胺基甲酸酯(甲基)丙烯酸酯樹脂為佳。 　　其中，就可得到低黏度之自由基聚合性樹脂組成物，硬化時之柔軟性的觀點而言，尤以包含聚醚多元醇的多元醇構造之胺基甲酸酯(甲基)丙烯酸酯樹脂更佳。聚醚多元醇，就自由基聚合性樹脂組成物之製作容易完成而言，較佳為聚乙二醇或聚丙二醇。 　　聚醚多元醇之重量平均分子量，較佳為500~5000、更佳為500~3000。重量平均分子量若為上述範圍內，則成為於胺基甲酸酯(甲基)丙烯酸酯樹脂中摻合了後述之自由基聚合性不飽和單體等的自由基聚合性樹脂組成物時，低黏度且相溶性良好。重量平均分子量之測定方法，係根據實施例測定。[Urethane (meth)acrylate resin] As the urethane (meth)acrylate resin, for example, both ends of a polyurethane obtained by reacting a polyisocyanate and a polyol can be used. The resin obtained by introducing the hydroxyl or isocyanate group into the (meth)acryloyl group. As the polyol, compounds described in "polyhydroxy compounds" or "polyols" described in Japanese Patent Laid-Open No. 2009-292890 and WO2016/171151 can be used without particular limitation. The polyhydric alcohol is not particularly limited, for example, polyester polyol, polyether polyol; dihydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, cyclohexane dimethanol; Dihydric alcohols such as adducts of dihydric alcohols represented by hydrogenated bisphenol A and the like and alkylene oxides represented by propylene oxide or ethylene oxide; 1,2,3,4-tetrahydroxybutane, Glycerol, trimethylolpropane, pentaerythritol and other alcohols with a valence of three or more. As the adduct of the above-mentioned dihydric alcohol and an alkylene oxide, for example, polyoxyalkylene bisphenol A ether can be mentioned. Among them, urethane (meth)acrylate resin, especially urethane containing polyol structure selected from polyester polyol, polyether polyol, polyoxyalkylene bisphenol A ether Ester (meth)acrylate resins are preferred. Among them, from the viewpoint of obtaining a low-viscosity radically polymerizable resin composition, and from the viewpoint of flexibility during curing, particularly, urethane (meth)acrylate resins having a polyol structure containing polyether polyols better. The polyether polyol is preferably polyethylene glycol or polypropylene glycol from the viewpoint of easy fabrication of the radically polymerizable resin composition. The weight average molecular weight of the polyether polyol is preferably 500-5000, more preferably 500-3000. When the weight average molecular weight is within the above-mentioned range, in the case of a radical polymerizable resin composition in which a radical polymerizable unsaturated monomer, etc., which will be described later, is blended with a urethane (meth)acrylate resin, it is low. Viscosity and good compatibility. The method for measuring the weight average molecular weight is based on the examples.

多元異氰酸酯，可列舉日本特開2009-292890號公報記載者或WO2016/171151號公報記載者，例如，可例示2,4-甲苯二異氰酸酯及其異構物、二苯基甲烷二異氰酸酯、六亞甲基二異氰酸酯、氫化伸二甲苯二異氰酸酯、異佛酮二異氰酸酯、伸二甲苯二異氰酸酯、二環己基甲烷二異氰酸酯、萘二異氰酸酯、三苯基甲烷三異氰酸酯等之化合物。此等之中，就合成樹脂時之反應性的觀點而言，尤以二苯基甲烷二異氰酸酯、異佛酮二異氰酸酯為佳。 　　導入(甲基)丙烯醯基時，例如可列舉使日本特開2009-292890號公報記載之含有羥基之(甲基)丙烯酸化合物與前述末端異氰酸基反應之方法，或使異氰酸2-(甲基)丙烯醯氧基乙酯、異氰酸2-(甲基)丙烯醯氧基丙酯、異氰酸1,1-雙(丙烯醯氧基甲基)乙酯等之含有異氰酸基之(甲基)丙烯酸化合物與前述末端羥基反應之方法。其中，就合成樹脂時的反應性之觀點而言，尤以使含有羥基之(甲基)丙烯酸化合物與末端異氰酸基反應之方法為佳。 　　就自由基聚合性樹脂組成物之柔軟性、密合性的觀點而言，含有羥基之(甲基)丙烯酸化合物，較佳為單官能(甲基)丙烯酸化合物之(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、己內酯改質(甲基)丙烯酸羥基烷酯、羥基乙基丙烯醯胺等，其中尤以(甲基)丙烯酸2-羥基乙酯或(甲基)丙烯酸2-羥基丙酯更佳。 　　胺基甲酸酯(甲基)丙烯酸酯樹脂之重量平均分子量，較佳為2000~22000、更佳為3000~19000、又更佳為4000 ~16000。重量平均分子量若為上述範圍內，則成為於胺基甲酸酯(甲基)丙烯酸酯樹脂中摻合了後述自由基聚合性不飽和單體等的自由基聚合性樹脂組成物時，低黏度且相溶性良好。The polyvalent isocyanates include those described in JP-A No. 2009-292890 or those described in WO2016/171151. For example, 2,4-toluene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate can be exemplified. Compounds of methyl diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc. Among these, from the viewpoint of reactivity at the time of synthesizing resin, diphenylmethane diisocyanate and isophorone diisocyanate are particularly preferred. When introducing a (meth)acryloyl group, for example, a method of reacting a hydroxyl group-containing (meth)acrylic compound described in Japanese Patent Laid-Open No. 2009-292890 with the above-mentioned terminal isocyanate group, or a method of reacting isocyanate 2 -(meth)acryloyloxyethyl ester, 2-(meth)acryloyloxypropyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, etc. containing isocyanide A method of reacting a (meth)acrylic compound of a cyano group with the aforementioned terminal hydroxyl group. Among them, a method of reacting a hydroxyl group-containing (meth)acrylic compound with a terminal isocyanate group is particularly preferable from the viewpoint of reactivity at the time of synthesizing resin. From the viewpoint of flexibility and adhesion of the radically polymerizable resin composition, the (meth)acrylic compound containing a hydroxyl group is preferably a (meth)acrylic 2-hydroxyl group of a monofunctional (meth)acrylic compound Ethyl ester, 2-hydroxypropyl (meth)acrylate, caprolactone modified hydroxyalkyl (meth)acrylate, hydroxyethyl acrylamide, etc., especially 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate is more preferred. The weight-average molecular weight of the urethane (meth)acrylate resin is preferably 2,000 to 22,000, more preferably 3,000 to 19,000, and still more preferably 4,000 to 16,000. When the weight average molecular weight is within the above-mentioned range, when it becomes a radical polymerizable resin composition in which a radical polymerizable unsaturated monomer, etc. described later is blended with a urethane (meth)acrylate resin, the viscosity is low. and good compatibility.

[乙烯酯樹脂] 　　乙烯酯樹脂，係使環氧化合物中所含有的環氧基之全部或一部分，與不飽和一元酸進行酯化反應而得者，於側鏈具有自由基反應性之碳-碳雙鍵。前述不飽和一元酸之代表例為(甲基)丙烯酸，因此稱為(甲基)丙烯酸環氧酯樹脂。 　　前述環氧化合物，可使用1分子內具有2個以上之環氧基的單體、寡聚物、聚合物全部，其分子量及分子構造並無特殊限定。例如，可列舉聯苯型環氧樹脂；雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、四溴雙酚A型環氧樹脂、四甲基雙酚F型環氧樹脂等之雙酚型環氧樹脂；二苯乙烯型環氧樹脂；酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等之酚醛清漆型環氧樹脂；三酚甲烷型環氧樹脂、烷基改質三酚甲烷型環氧樹脂等之多官能環氧樹脂；具有伸苯骨架之酚芳烷基型環氧樹脂、具有伸聯苯骨架之酚芳烷基型環氧樹脂等之酚芳烷基型環氧樹脂；二羥基萘型環氧樹脂、將二羥基萘之2聚體予以縮水甘油醚化而得之環氧樹脂等之萘酚型環氧樹脂；異三聚氰酸三縮水甘油酯、異三聚氰酸單烯丙基二縮水甘油酯等之含有三嗪核之環氧樹脂；脂環二環氧基縮醛、脂環二環氧基己二酸酯、脂環二環氧基羧酸酯、乙烯基環己烯二氧化物(vinylcyclohexene dioxide)等之脂環式聚環氧化合物；二環戊二烯改質酚型環氧樹脂等之橋聯環狀烴化合物改質酚型環氧樹脂；藉由二聚酸等之多元酸與表氯醇之反應而得之縮水甘油酯型環氧樹脂；使前述環氧樹脂與二異氰酸酯反應而得之含有噁唑啶酮環之環氧樹脂。 　　前述不飽和一元酸，可使用公知者。例如可列舉(甲基)丙烯酸、巴豆酸、桂皮酸等。此等之中尤以(甲基)丙烯酸為佳。 　　又，前述不飽和一元酸，亦可使用具有一個羥基與一個以上之(甲基)丙烯醯基的化合物，與多元酸酐之反應物。 　　前述多元酸酐，為用以使前述環氧樹脂之分子量增大者，可使用公知者。例如可列舉琥珀酸、戊二酸、己二酸、癸二酸、鄰苯二甲酸、富馬酸、馬來酸、依康酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、二聚酸、乙二醇/2莫耳馬來酸酐加成物、聚乙二醇/2莫耳馬來酸酐加成物、丙二醇/2莫耳馬來酸酐加成物、聚丙二醇/2莫耳馬來酸酐加成物、十二烷二酸、十三烷二酸、十八烷二酸、1,16-(6-乙基十六烷)二羧酸、1,12-(6-乙基十二烷)二羧酸、羧基末端丁二烯/丙烯腈共聚物(商品名Hycar CTBN)等之無水物。 　　上述乙烯酯樹脂之中，就韌性賦予、通用性、成本的觀點而言，尤以雙酚A型(甲基)丙烯酸環氧酯樹脂為佳。[Vinyl ester resin] Vinyl ester resin is obtained by esterifying all or a part of epoxy groups contained in epoxy compounds with unsaturated monobasic acid, and carbon- carbon double bond. The representative example of the aforementioned unsaturated monobasic acid is (meth)acrylic acid, so it is called (meth)acrylic epoxy ester resin. As the aforementioned epoxy compound, all monomers, oligomers, and polymers having two or more epoxy groups in one molecule can be used, and the molecular weight and molecular structure thereof are not particularly limited. For example, biphenyl type epoxy resins; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin, tetramethyl bisphenol Bisphenol type epoxy resin such as F type epoxy resin; stilbene type epoxy resin; novolac type epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc.; Polyfunctional epoxy resins such as epoxy resins, alkyl-modified trisphenol methane-type epoxy resins, etc.; Phenol aralkyl type epoxy resins such as oxygen resins; dihydroxynaphthalene type epoxy resins, epoxy resins obtained by etherifying a dimer of dihydroxynaphthalene with glycidyl ethers, etc. naphthol type epoxy resins; Epoxy resin containing triazine nucleus such as triglycidyl cyanurate and monoallyl diglycidyl isocyanurate; alicyclic diepoxy acetal, alicyclic diepoxy hexamethylene Alicyclic polyepoxy compounds such as acid esters, alicyclic diepoxycarboxylates, vinylcyclohexene dioxide, etc.; bridges of dicyclopentadiene-modified phenolic epoxy resins, etc. Bicyclic hydrocarbon compound-modified phenolic epoxy resin; glycidyl ester type epoxy resin obtained by reacting polybasic acid such as dimer acid with epichlorohydrin; obtained by reacting the aforementioned epoxy resin with diisocyanate The epoxy resin containing oxazolidinone ring. As the aforementioned unsaturated monobasic acid, a known one can be used. For example, (meth)acrylic acid, crotonic acid, cinnamic acid, etc. are mentioned. Among these, (meth)acrylic acid is particularly preferred. In addition, as the above-mentioned unsaturated monobasic acid, a compound having one hydroxyl group and one or more (meth)acryloyl groups and a reaction product of a polybasic acid anhydride can also be used. As the above-mentioned polybasic acid anhydride, a known one can be used for increasing the molecular weight of the above-mentioned epoxy resin. For example, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dihydrophthalic acid, Polyacid, ethylene glycol/2 mol maleic anhydride adduct, polyethylene glycol/2 mol maleic anhydride adduct, propylene glycol/2 mol maleic anhydride adduct, polypropylene glycol/2 mol Maleic anhydride adduct, dodecanedioic acid, tridecanedioic acid, octadecanedioic acid, 1,16-(6-ethylhexadecane)dicarboxylic acid, 1,12-(6-ethyl acetate) Anhydrous products such as dodecane) dicarboxylic acid, carboxyl-terminated butadiene/acrylonitrile copolymer (trade name Hycar CTBN). Among the above vinyl ester resins, bisphenol A-type (meth)acrylate epoxy ester resins are particularly preferred from the viewpoint of imparting toughness, versatility, and cost.

[不飽和聚酯樹脂] 　　不飽和聚酯樹脂，可使用使含有不飽和二元酸及依需要之飽和二元酸的二元酸成分，與多元醇成分進行酯化反應而得者。 　　前述不飽和二元酸和前述飽和二元酸，例如可列舉WO2016/171151號公報記載者等，此等可單獨、亦可組合2種以上使用。 　　前述多元醇並無特別限制，例如與胺基甲酸酯(甲基)丙烯酸酯樹脂的情況同樣地，可列舉WO2016/171151號公報記載者。[Unsaturated polyester resin] Unsaturated polyester resins can be obtained by esterifying a dibasic acid component containing an unsaturated dibasic acid and a saturated dibasic acid as needed with a polyol component. The unsaturated dibasic acid and the above-mentioned saturated dibasic acid include, for example, those described in WO2016/171151, and these may be used alone or in combination of two or more. The above-mentioned polyol is not particularly limited. For example, as in the case of the urethane (meth)acrylate resin, those described in WO2016/171151 can be cited.

不飽和聚酯，在不損及本發明之效果的範圍，亦可使用經二環戊二烯系化合物改質者。以二環戊二烯系化合物所進行之改質方法，例如可列舉得到二環戊二烯與馬來酸加成生成物後，使用其作為一元酸，導入二環戊二烯骨架之方法等之公知方法。 　　本發明中使用之乙烯酯樹脂或不飽和聚酯樹脂中，可導入烯丙基或苄基等之氧化聚合(空氣硬化)基。導入方法並無特別限制，例如，可列舉含有氧化聚合基之聚合物的添加，或具有羥基與烯丙基醚基之化合物的縮合；使具有羥基與烯丙基醚基之化合物與酸酐的反應物加成於烯丙基縮水甘油醚、2,6-二縮水甘油基苯基烯丙基醚之方法等。 　　再者，本發明中之氧化聚合(空氣硬化)，係指例如於烯丙基醚基等所見之藉由醚鍵與雙鍵之間的亞甲基鍵之氧化所致之過氧化物的生成與分解所伴隨之交聯。Unsaturated polyesters modified with a dicyclopentadiene-based compound can also be used within a range that does not impair the effects of the present invention. As a modification method with a dicyclopentadiene-based compound, for example, after obtaining an addition product of dicyclopentadiene and maleic acid, using it as a monobasic acid, and introducing a method of introducing a dicyclopentadiene skeleton, etc. known method. In the vinyl ester resin or unsaturated polyester resin used in the present invention, an oxidative polymerization (air hardening) group such as an allyl group or a benzyl group can be introduced. The introduction method is not particularly limited. For example, the addition of a polymer containing an oxidative polymerization group, the condensation of a compound having a hydroxyl group and an allyl ether group, and the reaction of a compound having a hydroxyl group and an allyl ether group with an acid anhydride can be mentioned. The method of adding compounds to allyl glycidyl ether, 2,6-diglycidyl phenyl allyl ether, etc. Furthermore, the oxidative polymerization (air hardening) in the present invention refers to the generation of peroxides caused by the oxidation of the methylene bond between the ether bond and the double bond, as seen in the allyl ether group, for example. and cross-linking that accompanies decomposition.

[聚酯(甲基)丙烯酸酯樹脂] 　　聚酯(甲基)丙烯酸酯樹脂，例如可使用使多元羧酸與多元醇反應而得之聚酯，具體而言，係對聚對苯二甲酸乙二酯等之兩末端的羥基，使(甲基)丙烯酸進行反應所得到之樹脂。[Polyester (meth)acrylate resin] As the polyester (meth)acrylate resin, for example, a polyester obtained by reacting a polyvalent carboxylic acid with a polyhydric alcohol can be used, and specifically, polyethylene terephthalate can be used. A resin obtained by reacting (meth)acrylic acid with hydroxyl groups at both ends such as diesters.

[(甲基)丙烯酸酯樹脂] 　　(甲基)丙烯酸酯樹脂，例如可使用具有由羥基、異氰酸基、羧基及環氧基中選出的1種以上之官能基的聚(甲基)丙烯酸樹脂，或對具有前述官能基之單體與(甲基)丙烯酸酯之共聚物的官能基，例如使具有羥基之(甲基)丙烯酸酯類進行反應而得到之樹脂。[(Meth)acrylate resin] As the (meth)acrylate resin, for example, poly(meth)acrylic acid having one or more functional groups selected from a hydroxyl group, an isocyanate group, a carboxyl group and an epoxy group can be used Resin, or the functional group of the copolymer of the monomer which has the said functional group, and (meth)acrylate, for example, the resin obtained by reacting the (meth)acrylate which has a hydroxyl group.

＜自由基聚合性不飽和單體(B)＞ 　　本發明中使用之自由基聚合性不飽和單體(B)，於降低自由基聚合性樹脂組成物之黏度，提高硬度、強度、耐藥品性、耐水性等上為重要。 　　前述自由基聚合性不飽和單體並無特別限制，較佳為具有(甲基)丙烯醯基、或乙烯基者。<Radical polymerizable unsaturated monomer (B)> The radical polymerizable unsaturated monomer (B) used in the present invention reduces the viscosity of the radical polymerizable resin composition and improves the hardness, strength, and chemical resistance , water resistance, etc. are important. The radically polymerizable unsaturated monomer is not particularly limited, but preferably has a (meth)acryloyl group or a vinyl group.

具有(甲基)丙烯醯基之單體可列舉丙烯酸酯、甲基丙烯酸酯等，可使用單官能性單體及多官能性單體。單官能性單體，具體而言，可例示(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸n-丁酯、(甲基)丙烯酸i-丁酯、(甲基)丙烯酸t-丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸二環戊烯氧基乙酯、乙二醇單甲基醚(甲基)丙烯酸酯、乙二醇單乙基醚(甲基)丙烯酸酯、乙二醇單丁基醚(甲基)丙烯酸酯、乙二醇單己基醚(甲基)丙烯酸酯、乙二醇單2-乙基己基醚(甲基)丙烯酸酯、二乙二醇單甲基醚(甲基)丙烯酸酯、二乙二醇單乙基醚(甲基)丙烯酸酯、二乙二醇單丁基醚(甲基)丙烯酸酯、二乙二醇單己基醚(甲基)丙烯酸酯、二乙二醇單2-乙基己基醚(甲基)丙烯酸酯、丙烯酸二環戊烯酯、丙烯酸二環戊烯氧基乙酯、丙烯酸三環癸酯、甲基丙烯酸三環癸酯、甲基丙烯酸二甲基胺基乙酯、甲基丙烯酸二乙基胺基乙酯等之化合物。 　　進一步地亦可例示己內酯改質(甲基)丙烯酸羥基烷酯、己內酯改質異三聚氰酸參(丙烯醯氧基烷基)酯等之化合物。就自由基聚合性樹脂組成物之黏度減低化的觀點而言，可例示具有己內酯加成莫耳數1~5(m=1~5)之聚己內酯(甲基)丙烯酸酯構造的單體。又，可例示具有己內酯之加成莫耳數為1~3之聚己內酯(甲基)丙烯酸酯構造的單體。其中尤以己內酯改質(甲基)丙烯酸羥基乙酯為佳。Acrylates, methacrylates, etc. are mentioned as the monomer which has a (meth)acryloyl group, and a monofunctional monomer and a polyfunctional monomer can be used. Monofunctional monomers, specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, (meth)acrylate base) t-butyl acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Stearyl ester, tridecyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, ethylene glycol monomethyl ether (methyl) Acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, ethylene glycol monohexyl ether (meth)acrylate, ethylene glycol mono 2- Ethylhexyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monobutyl ether ( Meth)acrylate, Diethylene glycol monohexyl ether (meth)acrylate, Diethylene glycol mono2-ethylhexyl ether (meth)acrylate, Dicyclopentenyl acrylate, Dicyclopentene acrylate Oxyethyl ester, tricyclodecyl acrylate, tricyclodecyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and other compounds. Further, compounds such as caprolactone-modified hydroxyalkyl (meth)acrylate and caprolactone-modified isocyanuric acid (acrylooxyalkyl) ester can also be exemplified. From the viewpoint of reducing the viscosity of the radically polymerizable resin composition, a polycaprolactone (meth)acrylate structure having a caprolactone addition molar number of 1 to 5 (m=1 to 5) can be exemplified. 's monomer. Moreover, the monomer which has the polycaprolactone (meth)acrylate structure whose added molar number of caprolactone is 1-3 can be illustrated. Among them, caprolactone-modified hydroxyethyl (meth)acrylate is particularly preferred.

多官能性單體，具體而言，可列舉新戊二醇二(甲基)丙烯酸酯、PTMG之二甲基丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、2-羥基1,3二甲基丙烯醯氧基丙烷、2,2-雙[4-(甲基丙烯醯基乙氧基)苯基]丙烷、2,2-雙[4-(甲基丙烯醯氧基･二乙氧基)苯基]丙烷、2,2-雙[4-(甲基丙烯醯氧基･聚乙氧基)苯基]丙烷、四乙二醇二丙烯酸酯、雙酚AEO改質(n=2)二丙烯酸酯、異三聚氰酸EO改質(n=3)二丙烯酸酯、季戊四醇二丙烯酸酯單硬脂酸酯等。Specifically, polyfunctional monomers include neopentyl glycol di(meth)acrylate, PTMG dimethacrylate, 1,3-butanediol di(meth)acrylate, 1,6-butanediol di(meth)acrylate, -Hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-hydroxyl,3-dimethylacryloyloxypropane, 2,2-bis[4-(methyl) Acryloylethoxy)phenyl]propane, 2,2-bis[4-(methacryloyloxy・diethoxy)phenyl]propane, 2,2-bis[4-(methpropene] Ethyloxy･polyethoxy)phenyl]propane, tetraethylene glycol diacrylate, bisphenol AEO modified (n=2) diacrylate, isocyanuric acid EO modified (n=3) diacrylate Acrylates, pentaerythritol diacrylate monostearate, etc.

進一步地，多官能性單體，可例示乙二醇二(甲基)丙烯酸酯、1,2-丙二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯等之烷二醇二-(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、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯等之聚氧化烯-二醇二(甲基)丙烯酸酯； 　　三羥甲基丙烷二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、(甲基)丙烯酸烯丙酯、富馬酸二烯丙酯； 　　其他化合物，可例示參(2-羥基乙基)異三聚氰酸丙烯酸酯等。Further, as the polyfunctional monomer, ethylene glycol di(meth)acrylate, 1,2-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, Alkanediol di-(meth)acrylates such as 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc. base) acrylate; diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate , Polyoxyalkylene-diol di(meth)acrylate such as polyethylene glycol di(meth)acrylate; Trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, Pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(meth)acrylate Pentaerythritol hexa(meth)acrylate, allyl (meth)acrylate, diallyl fumarate; As other compounds, ginseng (2-hydroxyethyl) isocyanurate acrylate and the like can be exemplified.

具有乙烯基之單體的具體例子，可列舉苯乙烯、p-氯苯乙烯、乙烯基甲苯、α-甲基苯乙烯、二氯苯乙烯、二乙烯基苯、t-丁基苯乙烯、乙酸乙烯酯、鄰苯二甲酸二烯丙酯、鄰苯二甲酸三烯丙酯、異三聚氰酸三烯丙酯乙烯基苄基丁基醚、乙烯基苄基己基醚、乙烯基苄基辛基醚、乙烯基苄基-(2-乙基己基)醚、乙烯基苄基(β-甲氧基甲基)醚、乙烯基苄基(n-丁氧基丙基)醚、乙烯基苄基環己基醚、乙烯基苄基-(β-苯氧基乙基)醚、乙烯基苄基二環戊烯基醚、乙烯基苄基二環戊烯氧基乙基醚、乙烯基苄基二環戊烯基甲基醚、二乙烯基苄基醚。 　　此等可單獨亦可組合2種以上使用。Specific examples of the monomer having a vinyl group include styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, acetic acid Vinyl ester, diallyl phthalate, triallyl phthalate, triallyl isocyanurate, vinylbenzylbutyl ether, vinylbenzylhexyl ether, vinylbenzyloctyl Ethyl ether, vinylbenzyl-(2-ethylhexyl) ether, vinylbenzyl (β-methoxymethyl) ether, vinylbenzyl (n-butoxypropyl) ether, vinylbenzyl Cyclohexyl ether, vinylbenzyl-(β-phenoxyethyl) ether, vinylbenzyl dicyclopentenyl ether, vinylbenzyl dicyclopentenyloxyethyl ether, vinylbenzyl Dicyclopentenyl methyl ether, divinylbenzyl ether. These can be used alone or in combination of two or more.

就成本、稀釋性之觀點而言，上述自由基聚合性不飽和單體(B)成分，較佳為(甲基)丙烯酸甲酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、苯乙烯。From the viewpoint of cost and diluting property, the above-mentioned radical polymerizable unsaturated monomer (B) component is preferably methyl (meth)acrylate, phenoxyethyl (meth)acrylate, (meth)acrylate 2-ethylhexyl acrylate, lauryl (meth)acrylate, styrene.

本發明之自由基聚合性樹脂組成物中，相對於(A)成分與(B)成分之合計量而言，(A)成分之含量，較佳為5~95質量%、更佳為15~85質量%、又更佳為25~75質量%。相對於(A)成分與(B)成分之合計量而言，(A)成分之含量若為上述範圍內，則可得到良好之作業性。In the radically polymerizable resin composition of the present invention, the content of the (A) component is preferably 5 to 95% by mass, more preferably 15 to 15% by mass relative to the total amount of the (A) component and the (B) component. 85 mass %, and more preferably 25 to 75 mass %. With respect to the total amount of (A) component and (B) component, if content of (A) component is in the said range, favorable workability|operativity can be acquired.

＜胺系硬化促進劑(C)＞ 　　本發明所用的胺系硬化促進劑(C)，可無特殊限制地使用公知之胺類，具體而言，可使用苯胺、N,N-二甲基苯胺、N,N-二乙基苯胺、p-甲苯胺、N,N-二甲基-p-甲苯胺、N,N-雙(2-羥基乙基)-p-甲苯胺、4-(N,N-二甲基胺基)苯甲醛、4-[N,N-雙(2-羥基乙基)胺基]苯甲醛、4-(N-甲基-N-羥基乙基胺基)苯甲醛、N,N-雙(2-羥基丙基)-p-甲苯胺、N-乙基-m-甲苯胺、三乙醇胺、m-甲苯胺、二乙三胺、吡啶、苯基嗎啉、哌啶、N,N-雙(2-羥基乙基)苯胺、二乙醇苯胺、2,4,6-參(二甲基胺基甲基)酚、N,N-二甲基苄胺等之胺類等。其中，就容易促進硬化之觀點而言，尤較佳為芳香族3級胺類。具體而言，較佳為N,N-二甲基苯胺、N,N-二甲基-p-甲苯胺、N,N-雙(2-羥基乙基)-p-甲苯胺、N,N-雙(2-羥基丙基)-p-甲苯胺、N,N-雙(2-羥基乙基)苯胺。又，其中，尤更佳為含有羥基之芳香族3級胺。具體而言，較佳為N,N-雙(2-羥基乙基)-p-甲苯胺、N,N-雙(2-羥基丙基)-p-甲苯胺、N,N-雙(2-羥基乙基)苯胺。 　　胺系硬化促進劑(C)之含量，相對於(A)自由基聚合性樹脂及(B)自由基聚合性不飽和單體之合計100質量份而言，較佳為0.01~10質量份、更佳為0.05~5.0質量份、又更佳為0.1~3.0質量份。含量為上述範圍內時，硬化性之調整容易。<Amine-based curing accelerator (C)> As the amine-based curing accelerator (C) used in the present invention, known amines can be used without particular limitation, and specifically, aniline, N,N-dimethylaniline can be used , N,N-diethylaniline, p-toluidine, N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, 4-(N ,N-dimethylamino)benzaldehyde, 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, 4-(N-methyl-N-hydroxyethylamino)benzene Formaldehyde, N,N-bis(2-hydroxypropyl)-p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, Piperidine, N,N-bis(2-hydroxyethyl)aniline, diethanolaniline, 2,4,6-sam(dimethylaminomethyl)phenol, N,N-dimethylbenzylamine, etc. Amines, etc. Among them, aromatic tertiary amines are particularly preferred from the viewpoint of promoting hardening easily. Specifically, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N- -Bis(2-hydroxypropyl)-p-toluidine, N,N-bis(2-hydroxyethyl)aniline. In addition, among them, an aromatic tertiary amine containing a hydroxyl group is more preferable. Specifically, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxypropyl)-p-toluidine, N,N-bis(2 -Hydroxyethyl)aniline. The content of the amine-based curing accelerator (C) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer, More preferably, it is 0.05-5.0 mass parts, More preferably, it is 0.1-3.0 mass parts. When the content is within the above-mentioned range, the adjustment of curability is easy.

＜多官能硫醇化合物(D)＞ 　　本發明所用的多官能硫醇化合物(D)，為具有複數個巰基之化合物，其係由1級硫醇化合物(D1)、2級硫醇化合物(D2)及3級硫醇化合物(D3)中選出的化合物。此等可1種單獨使用、亦可合併使用2種以上。就保存安定性及臭氣之觀點而言，較佳為2級或3級之硫醇化合物。 　　此處，「1級硫醇化合物」，係指具有鍵結於1級碳原子之巰基的化合物，同樣地，「2級硫醇化合物」，係指具有鍵結於2級碳原子之巰基的化合物，又，「3級硫醇化合物」，係指具有鍵結於3級碳原子之巰基的化合物。再者，本發明中，2級硫醇化合物，即使具有鍵結於1級碳原子之巰基的情況，該化合物亦視為2級硫醇化合物(D2)。同樣地，3級硫醇化合物，即使具有鍵結於1級碳原子之巰基及鍵結於2級碳原子之巰基的至少任1個以上的情況，該化合物亦視為3級硫醇化合物(D3)。 　　因此，本發明所用的前述1級硫醇化合物(D1)、2級硫醇化合物(D2)及3級硫醇化合物(D3)，為化合物中具有複數個巰基之硫醇化合物。硫醇化合物中之巰基數，通常為2~10個左右，特別藉由使用巰基數為具有2~6個之硫醇化合物，可減低樹脂組成物硬化後之臭氣性。<Polyfunctional thiol compound (D)> The polyfunctional thiol compound (D) used in the present invention is a compound having a plurality of mercapto groups, and is composed of a first-order thiol compound (D1), a second-order thiol compound (D2) ) and a compound selected from the tertiary thiol compound (D3). These may be used individually by 1 type, and may use 2 or more types together. From the viewpoints of storage stability and odor, a mercaptan compound of second or third order is preferred. Here, the "primary thiol compound" refers to a compound having a mercapto group bonded to a primary carbon atom, and similarly, a "secondary thiol compound" refers to a compound having a mercapto group bonded to a secondary carbon atom. The compound, also, "tertiary thiol compound" refers to a compound having a mercapto group bonded to a tertiary carbon atom. Furthermore, in the present invention, even when the secondary thiol compound has a mercapto group bonded to the primary carbon atom, the compound is regarded as the secondary thiol compound (D2). Similarly, a tertiary thiol compound is regarded as a tertiary thiol compound even if it has at least one of a mercapto group bound to a first-order carbon atom and a mercapto group bound to a second-order carbon atom ( D3). Therefore, the aforementioned first-order thiol compound (D1), second-order thiol compound (D2) and third-order thiol compound (D3) used in the present invention are thiol compounds having a plurality of mercapto groups in the compound. The number of mercapto groups in the thiol compound is usually about 2 to 10. In particular, by using a thiol compound having 2 to 6 mercapto groups, the odor of the resin composition after curing can be reduced.

本發明所用的多官能硫醇化合物(D)，較佳為具有下述通式(Q)表示之構造的化合物。

Figure 02_image005
上述通式(Q)中，R1 及R2 ，係分別獨立地為氫原子、碳數1~10之烷基或碳數6~18之芳香族基。*表示係連結於具有至少1個巰基之任意有機基。a為0~2之整數。The polyfunctional thiol compound (D) used in the present invention is preferably a compound having a structure represented by the following general formula (Q).
Figure 02_image005
In the above general formula (Q), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. * indicates that it is linked to any organic group having at least one mercapto group. a is an integer from 0 to 2.

上述通式(Q)表示之多官能硫醇化合物(D)之中，尤佳為具有下述通式(Q-1)表示之構造者。

Figure 02_image007
上述通式(Q-1)中，R1 及R2 ，係分別獨立地為氫原子、碳數1~10之烷基或碳數6~18之芳香族基。**表示係連結於具有至少1個巰基之任意有機基。a為0~2之整數。Among the polyfunctional thiol compounds (D) represented by the general formula (Q), those having a structure represented by the following general formula (Q-1) are particularly preferred.
Figure 02_image007
In the above general formula (Q-1), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. ** indicates that it is linked to any organic group having at least one mercapto group. a is an integer from 0 to 2.

上述通式(Q)及通式(Q-1)表示之多官能硫醇化合物(D)之中，尤更佳為下述通式(S)表示之含有巰基之羧酸，與多元醇的酯化合物。如此之化合物，可藉由使含有巰基之羧酸與多元醇以公知方法進行酯化反應而得到。Among the polyfunctional thiol compounds (D) represented by the general formula (Q) and the general formula (Q-1), the mercapto-group-containing carboxylic acid represented by the following general formula (S) is particularly preferred, and the compound of the polyhydric alcohol ester compound. Such a compound can be obtained by subjecting a mercapto group-containing carboxylic acid to an esterification reaction with a polyhydric alcohol by a known method.

Figure 02_image009
(通式(S)中，R3 為氫原子、碳數1~10之烷基、或碳數6~18之芳香族基，R4 為碳數1~10之烷基或碳數6~18之芳香族基。a為0~2之整數)。
Figure 02_image009
(In the general formula (S), R 3 is a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an aromatic group with 6 to 18 carbon atoms, and R 4 is an alkyl group with 1 to 10 carbon atoms or an alkyl group with 6 to 10 carbon atoms. The aromatic group of 18. a is an integer of 0~2).

前述通式(S)表示之含有巰基之羧酸，為來自2級硫醇化合物(D2)之化合物時，具體而言，可列舉2-巰基丙酸、3-巰基丁酸、3-巰基-3-苯基丙酸等。 　　又，為來自3級硫醇化合物(D3)之化合物時，具體而言，可列舉2-巰基異丁酸、3-巰基-3-甲基丁酸等。When the mercapto group-containing carboxylic acid represented by the aforementioned general formula (S) is a compound derived from the secondary thiol compound (D2), specifically, 2-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercapto- 3-phenylpropionic acid, etc. In addition, in the case of a compound derived from the tertiary thiol compound (D3), specific examples thereof include 2-mercaptoisobutyric acid, 3-mercapto-3-methylbutyric acid, and the like.

前述多元醇，可列舉乙二醇、二乙二醇、三乙二醇、四乙二醇、聚乙二醇、丙二醇、二丙二醇、三丙二醇、聚丙二醇、新戊二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,2-戊二醇、1,3-戊二醇、2,3-戊二醇、1,4-戊二醇、1,5-戊二醇、1,6-己二醇、1,9-壬二醇、三環癸烷二甲醇、2,2-雙(2-羥基乙氧基苯基)丙烷、雙酚A環氧烷加成物、雙酚F環氧烷加成物、雙酚S環氧烷加成物、1,4-環己二醇、1,4-環己烷二甲醇、1,2-己二醇、1,3-己二醇、2,3-己二醇、1,4-己二醇、2,4-己二醇、3,4-己二醇、1,5-己二醇、2,5-己二醇、1,6-己二醇、9,9-雙[4-(2-羥基乙基)苯基]茀等之2元醇；甘油、二甘油、三羥甲基乙烷、三羥甲基丙烷、二-三羥甲基丙烷、異三聚氰酸參(2-羥基乙酯)、己三醇、山梨醇、季戊四醇、二季戊四醇、蔗糖、2,2-雙(2,3-二羥基丙氧基苯基)丙烷等之3元以上之醇；其他可列舉聚碳酸酯二醇、二聚酸聚酯多元醇等。The aforementioned polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,2- Propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 1, 4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, tricyclodecane dimethanol, 2,2-bis(2-hydroxyethoxybenzene) base) propane, bisphenol A alkylene oxide adduct, bisphenol F alkylene oxide adduct, bisphenol S alkylene oxide adduct, 1,4-cyclohexanediol, 1,4-cyclohexane Dimethanol, 1,2-Hexanediol, 1,3-Hexanediol, 2,3-Hexanediol, 1,4-Hexanediol, 2,4-Hexanediol, 3,4-Hexanediol , 1,5-Hexanediol, 2,5-Hexanediol, 1,6-Hexanediol, 9,9-bis[4-(2-hydroxyethyl)phenyl]diol, etc.; Glycerin, Diglycerol, Trimethylolethane, Trimethylolpropane, Di-trimethylolpropane, Isocyanurate (2-Hydroxyethyl Ester), Hexylene Triol, Sorbitol, Pentaerythritol, Dimethylol Trivalent or higher alcohols such as pentaerythritol, sucrose, 2,2-bis(2,3-dihydroxypropoxyphenyl)propane; others include polycarbonate diol, dimer acid polyester polyol, and the like.

此等之中，就獲得容易性或在濕潤條件下亦發揮硬化促進能力的觀點而言，較佳為乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇等之2元醇；甘油、三羥甲基乙烷、三羥甲基丙烷、異三聚氰酸參(2-羥基乙酯)、季戊四醇、二季戊四醇、2,2-雙(2,3-二羥基丙氧基苯基)丙烷等之3元以上之醇；聚碳酸酯二醇、二聚酸聚酯多元醇；就官能基數及蒸氣壓之觀點而言，更佳為1,4-丁二醇、三羥甲基乙烷、三羥甲基丙烷、異三聚氰酸參(2-羥基乙酯)、季戊四醇、聚碳酸酯二醇、二聚酸聚酯多元醇。Among these, ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4-butanediol are preferred from the viewpoints of availability and the ability to promote hardening even under wet conditions Dihydric alcohols such as; glycerin, trimethylolethane, trimethylolpropane, isocyanurate (2-hydroxyethyl ester), pentaerythritol, dipentaerythritol, 2,2-bis(2,3- Tri- or higher-valent alcohols such as dihydroxypropoxyphenyl)propane; polycarbonate diol, dimer acid polyester polyol; more preferably 1,4-butane from the viewpoint of the number of functional groups and vapor pressure Diol, trimethylolethane, trimethylolpropane, isocyanuric acid ginseng (2-hydroxyethyl ester), pentaerythritol, polycarbonate diol, dimer acid polyester polyol.

[1級硫醇化合物(D1)] 　　1級硫醇化合物(D1)，具體而言，可列舉三羥甲基丙烷參硫代丙酸酯、異三聚氰酸參-[(3-巰基丙醯氧基)-乙酯]、季戊四醇肆(3-巰基丙酸酯)、四乙二醇雙(3-巰基丙酸酯)、二季戊四醇陸(3-巰基丙酸酯)等。 　　1級硫醇化合物(D1)當中，分子中具有2個以上之1級巰基的化合物之市售品，適合使用季戊四醇肆(3-巰基丙酸酯)(SC有機化學(股)製、製品名：PEMP)、三羥甲基丙烷參硫代丙酸酯(淀化學(股)製、製品名：TMTP)等。[First-order thiol compound (D1)] The first-order thiol compound (D1), specifically, trimethylolpropane thiopropionate, isocyanuric acid bis-[(3-mercaptopropionate, Ethyloxy)-ethyl ester], pentaerythritol (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol (3-mercaptopropionate) and the like. Among the first-order thiol compounds (D1), commercially available compounds having two or more first-order mercapto groups in the molecule are suitable for use with pentaerythritol (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd., product name : PEMP), trimethylolpropane thiopropionate (manufactured by Yodo Chemical Co., Ltd., product name: TMTP), etc.

[2級硫醇化合物(D2)] 　　2級硫醇化合物(D2)，具體而言，可列舉3-巰基鄰苯二甲酸二(1-巰基乙酯)、鄰苯二甲酸二(2-巰基丙酯)、鄰苯二甲酸二(3-巰基丁酯)、乙二醇雙(3-巰基丁酸酯)、丙二醇雙(3-巰基丁酸酯)、二乙二醇雙(3-巰基丁酸酯)、丁二醇雙(3-巰基丁酸酯)、辛二醇雙(3-巰基丁酸酯)、三羥甲基乙烷參(3-巰基丁酸酯)、三羥甲基丙烷參(3-巰基丁酸酯)、季戊四醇肆(3-巰基丁酸酯)、二季戊四醇陸(3-巰基丁酸酯)、乙二醇雙(2-巰基丙酸酯)、丙二醇雙(2-巰基丙酸酯)、二乙二醇雙(2-巰基丙酸酯)、丁二醇雙(2-巰基丙酸酯)、辛二醇雙(2-巰基丙酸酯)、三羥甲基丙烷參(2-巰基丙酸酯)、季戊四醇肆(2-巰基丙酸酯)、二季戊四醇陸(2-巰基丙酸酯)、乙二醇雙(4-巰基戊酸酯)、二乙二醇雙(4-巰基戊酸酯)、丁二醇雙(4-巰基戊酸酯)、辛二醇雙(4-巰基戊酸酯)、三羥甲基丙烷參(4-巰基戊酸酯)、季戊四醇肆(4-巰基戊酸酯)、二季戊四醇陸(4-巰基戊酸酯)、乙二醇雙(3-巰基戊酸酯)、丙二醇雙(3-巰基戊酸酯)、二乙二醇雙(3-巰基戊酸酯)、丁二醇雙(3-巰基戊酸酯)、辛二醇雙(3-巰基戊酸酯)、三羥甲基丙烷參(3-巰基戊酸酯)、季戊四醇肆(3-巰基戊酸酯)、二季戊四醇陸(3-巰基戊酸酯)、氫化雙酚A雙(3-巰基丁酸酯)、4,4’-(9-亞茀基)雙(2-苯氧基乙基(3-巰基丁酸酯))、乙二醇雙(3-巰基-3-苯基丙酸酯)、丙二醇雙(3-巰基-3-苯基丙酸酯)、二乙二醇雙(3-巰基-3-苯基丙酸酯)、丁二醇雙(3-巰基-3-苯基丙酸酯)、辛二醇雙(3-巰基-3-苯基丙酸酯)、三羥甲基丙烷參(3-巰基-3-苯基丙酸酯)、異三聚氰酸參-2-(3-巰基-3-苯基丙酸酯)乙酯、季戊四醇肆(3-巰基-3-苯基丙酸酯)、二季戊四醇陸(3-巰基-3-苯基丙酸酯)、1,3,5-參[2-(3-巰基丁醯氧基乙基)]-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮等。[Second-order thiol compound (D2)] The second-order thiol compound (D2), specifically, 3-mercaptophthalate bis(1-mercaptoethyl ester), phthalate bis(2-mercaptoethyl ester), propyl ester), bis(3-mercaptobutyl phthalate), ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate) butyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate), trimethylolethane ginseng (3-mercaptobutyrate), trimethylol Propane ginseng (3-mercaptobutyrate), pentaerythritol bismuth (3-mercaptobutyrate), dipentaerythritol bismuth (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate), octanediol bis(2-mercaptopropionate), tris Methylol propane ginseng (2-mercaptopropionate), pentaerythritol tetra (2-mercaptopropionate), dipentaerythritol (2-mercaptopropionate), ethylene glycol bis (4-mercaptovalerate), Diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate), trimethylolpropane bis(4-mercaptovalerate) valerate), pentaerythritol (4-mercaptovalerate), dipentaerythritol (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate) ), diethylene glycol bis(3-mercaptovalerate), butanediol bis(3-mercaptovalerate), octanediol bis(3-mercaptovalerate), trimethylolpropane ginseng (3 -Mercaptovalerate), Pentaerythritol (3-Mercaptovalerate), Dipentaerythritol (3-Mercaptovalerate), Hydrogenated Bisphenol A Bis(3-Mercaptobutyrate), 4,4'-( 9-Pylylene) bis(2-phenoxyethyl(3-mercaptobutyrate)), ethylene glycol bis(3-mercapto-3-phenylpropionate), propylene glycol bis(3-mercapto- 3-phenylpropionate), diethylene glycol bis(3-mercapto-3-phenylpropionate), butanediol bis(3-mercapto-3-phenylpropionate), octanediol bis (3-mercapto-3-phenylpropionate), trimethylolpropane (3-mercapto-3-phenylpropionate), isocyanuric acid-2-(3-mercapto-3- phenylpropionate) ethyl ester, pentaerythritol tetra (3-mercapto-3-phenylpropionate), dipentaerythritol (3-mercapto-3-phenylpropionate), 1,3,5-para[ 2-(3-Mercaptobutanoyloxyethyl)]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, etc.

2級硫醇化合物(D2)當中，分子中具有2個以上之2級巰基的化合物之市售品，適合使用1,4-雙(3-巰基丁醯氧基)丁烷(昭和電工(股)製「Karenz MT(註冊商標)BD1」)、季戊四醇肆(3-巰基丁酸酯)(昭和電工(股)製「Karenz MT(註冊商標)PE1」)、1,3,5-參[2-(3-巰基丁醯氧基乙基)]-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮(昭和電工(股)製「Karenz MT(註冊商標)NR1」)、三羥甲基乙烷參(3-巰基丁酸酯)(昭和電工(股)製「TEMB」)、三羥甲基丙烷參(3-巰基丁酸酯)(昭和電工(股)製「TPMB」)等。Among the second-order thiol compounds (D2), commercially available compounds having two or more second-order mercapto groups in the molecule are preferably 1,4-bis(3-mercaptobutanoyloxy)butane (Showa Denko Co., Ltd. ) "Karenz MT (registered trademark) BD1"), pentaerythritol (3-mercaptobutyrate) (Showa Denko Co., Ltd. "Karenz MT (registered trademark) PE1"), 1,3,5-gin [2 -(3-Mercaptobutanoyloxyethyl)]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko Co., Ltd. "Karenz MT (registered) Trademark) NR1"), Trimethylolethane ginseng (3-mercaptobutyrate) ("TEMB" manufactured by Showa Denko Co., Ltd.), Trimethylolpropane ginseng (3-mercaptobutyrate) (Showa Denko Co., Ltd.) (stock) system "TPMB"), etc.

[3級硫醇化合物(D3)] 　　3級硫醇化合物(D3)，具體而言，可列舉鄰苯二甲酸二(2-巰基異丁酯)、乙二醇雙(2-巰基異丁酸酯)、丙二醇雙(2-巰基異丁酸酯)、二乙二醇雙(2-巰基異丁酸酯)、丁二醇雙(2-巰基異丁酸酯)、辛二醇雙(2-巰基異丁酸酯)、三羥甲基乙烷參(2-巰基異丁酸酯)、三羥甲基丙烷參(2-巰基異丁酸酯)、季戊四醇肆(2-巰基異丁酸酯)、二季戊四醇陸(2-巰基異丁酸酯)、鄰苯二甲酸二(3-巰基-3-甲基丁酯)、乙二醇雙(3-巰基-3-甲基丁酸酯)、丙二醇雙(3-巰基-3-甲基丁酸酯)、二乙二醇雙(3-巰基-3-甲基丁酸酯)、丁二醇雙(3-巰基-3-甲基丁酸酯)、辛二醇雙(3-巰基-3-甲基丁酸酯)、三羥甲基乙烷參(3-巰基-3-甲基丁酸酯)、三羥甲基丙烷參(3-巰基-3-甲基丁酸酯)、季戊四醇肆(3-巰基-3-甲基丁酸酯)、二季戊四醇陸(3-巰基-3-甲基丁酸酯)等。[Third-level thiol compound (D3)] The third-level thiol compound (D3), specifically, bis(2-mercaptoisobutyl phthalate), ethylene glycol bis(2-mercaptoisobutyric acid) can be mentioned ester), propylene glycol bis(2-mercaptoisobutyrate), diethylene glycol bis(2-mercaptoisobutyrate), butanediol bis(2-mercaptoisobutyrate), octanediol bis(2 -Mercaptoisobutyrate), Trimethylolethane (2-mercaptoisobutyrate), Trimethylolpropane (2-mercaptoisobutyrate), Pentaerythritol (2-mercaptoisobutyrate) ester), dipentaerythritol (2-mercaptoisobutyrate), bis(3-mercapto-3-methylbutyl phthalate), ethylene glycol bis(3-mercapto-3-methylbutyrate) ), propylene glycol bis(3-mercapto-3-methyl butyrate), diethylene glycol bis(3-mercapto-3-methyl butyrate), butanediol bis(3-mercapto-3-methyl butyrate) Butyrate), octanediol bis(3-mercapto-3-methylbutyrate), trimethylolethane ginseng (3-mercapto-3-methylbutyrate), trimethylolpropane ginseng (3-mercapto-3-methylbutyrate), pentaerythritol (3-mercapto-3-methylbutyrate), dipentaerythritol (3-mercapto-3-methylbutyrate), and the like.

多官能硫醇化合物(D)之含量，相對於(A)自由基聚合性樹脂及(B)自由基聚合性不飽和單體之合計100質量份而言，較佳為0.1~20質量份、更佳為0.3~15質量份。含量若為0.1質量份以上，則可充分發揮低溫硬化性、密合性提高等之效果。又，含量若為20質量份以下，則可充分保持使樹脂組成物硬化時的強度，適合作為構造物之補修材用途。The content of the polyfunctional thiol compound (D) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer, More preferably, it is 0.3-15 mass parts. When the content is 0.1 part by mass or more, effects such as low temperature sclerosis and adhesion improvement can be sufficiently exhibited. Moreover, when content is 20 mass parts or less, the intensity|strength at the time of hardening a resin composition can be fully maintained, and it is suitable for use as a repair material of a structure.

＜硬化劑(E)＞ 　　本發明之自由基聚合性樹脂組成物，亦可含有硬化劑(E)。本發明所用的(E)硬化劑並無特殊限定，可使用公知之自由基聚合起始劑，較佳使用有機化過氧化物。 　　有機過氧化物之例子，可列舉酮過氧化物、過氧苯甲酸酯、氫過氧化物、二醯基過氧化物、過氧基縮酮、氫過氧化物、二烯丙基過氧化物、過氧基酯及過氧基二碳酸酯等。更具體而言，可使用甲基乙基酮過氧化物、異丙苯氫過氧化物、過氧苯甲酸t-丁酯、二苯甲醯基過氧化物(亦稱為苯甲醯基過氧化物)、苯甲醯基m-甲基苯甲醯基過氧化物、m-甲苯甲醯基過氧化物、二異丙苯基過氧化物、二異丙基過氧化物、二-t-丁基過氧化物、過氧苯甲酸t-丁酯、1,1-雙(t-丁基過氧基)-3,3,5-三甲基環己烷、2,5-二甲基-2,5-雙(t-丁基過氧基)己炔-3、3-異丙基氫過氧化物、t-丁基氫過氧化物、二異丙苯基氫過氧化物、乙醯基過氧化物、過氧基二碳酸雙(4-t-丁基環己酯)、過氧基二碳酸二異丙酯、異丁基過氧化物、3,3,5-三甲基己醯基過氧化物、月桂基過氧化物等。又，硬化劑亦可使用偶氮化合物等，具體而言可列舉偶氮雙異丁腈及偶氮雙碳醯胺等。此等有機過氧化物、偶氮化合物，可單獨或組合來使用。又，此等之中，就獲得之容易性的觀點而言，尤以二苯甲醯基過氧化物、苯甲醯基m-甲基苯甲醯基過氧化物、m-甲苯甲醯基過氧化物、甲基乙基酮過氧化物、異丙苯氫過氧化物、過氧苯甲酸t-丁酯為佳。就硬化時不易受水分影響的觀點而言，更佳為二苯甲醯基過氧化物、苯甲醯基m-甲基苯甲醯基過氧化物、m-甲苯甲醯基過氧化物。<Curing agent (E)> The radically polymerizable resin composition of the present invention may contain a curing agent (E). The (E) hardener used in the present invention is not particularly limited, and a known radical polymerization initiator can be used, and an organic peroxide is preferably used. Examples of organic peroxides include ketone peroxides, peroxybenzoates, hydroperoxides, diacyl peroxides, peroxy ketals, hydroperoxides, diallyl peroxides compounds, peroxyesters and peroxydicarbonates, etc. More specifically, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl peroxybenzoate, dibenzyl peroxide (also known as benzyl peroxide) can be used. oxide), benzyl m-methylbenzyl peroxide, m-methylbenzyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t -Butyl peroxide, t-butyl peroxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl base-2,5-bis(t-butylperoxy)hexyn-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl hydroperoxide, Acetyl peroxide, bis(4-t-butylcyclohexyl peroxydicarbonate), diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethyl Hexyl peroxide, lauryl peroxide, etc. Moreover, an azo compound etc. can also be used as a hardening|curing agent, Specifically, azobisisobutyronitrile, azobiscarbamide, etc. are mentioned. These organic peroxides and azo compounds can be used alone or in combination. In addition, among these, from the viewpoint of availability, in particular, dibenzoyl peroxide, benzyl m-methylbenzyl peroxide, m-tolylyl peroxide, Peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl peroxybenzoate are preferred. From the viewpoint of being less susceptible to moisture at the time of hardening, dibenzoyl peroxide, benzyl m-methylbenzyl peroxide, and m-tolyl peroxide are more preferred.

硬化劑(E)之摻合量，相對於上述(A)成分與(B)成分之合計100質量份而言，較佳為0.1~10質量份、更佳為0.3~8質量份、又更佳為0.5~6質量份。硬化劑(E)之摻合量為0.1質量份以上時，容易得到所期望之硬化性。另一方面，硬化劑(E)之摻合量為10質量份以下時，於經濟上有利，容易得到充分的作業時間。The blending amount of the curing agent (E) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 8 parts by mass, and more preferably 100 parts by mass of the total of the above-mentioned (A) component and (B) component. It is preferably 0.5 to 6 parts by mass. When the compounding quantity of a hardening|curing agent (E) is 0.1 mass part or more, desired hardenability is easy to be obtained. On the other hand, when the compounding quantity of a hardening|curing agent (E) is 10 mass parts or less, it is economically advantageous, and it becomes easy to obtain sufficient working time.

＜其他成分＞ [聚合抑制劑] 　　本發明之自由基聚合性樹脂組成物，就抑制(A)自由基聚合性樹脂及(B)自由基聚合性不飽和單體之過度聚合的觀點、控制反應速度之觀點而言，亦可含有聚合抑制劑。 　　聚合抑制劑，可列舉氫醌、甲基氫醌、酚噻嗪、兒茶酚、4-tert-丁基兒茶酚等之公知者。<Other components> [Polymerization inhibitor] The radical polymerizable resin composition of the present invention controls the reaction from the viewpoint of suppressing excessive polymerization of (A) the radical polymerizable resin and (B) the radical polymerizable unsaturated monomer From the viewpoint of speed, a polymerization inhibitor may be contained. As the polymerization inhibitor, known ones such as hydroquinone, methylhydroquinone, phenothiazine, catechol, and 4-tert-butylcatechol can be mentioned.

[胺系以外之硬化促進劑] 　　本發明之自由基聚合性樹脂組成物中，亦可含有上述胺系硬化促進劑以外之硬化促進劑。胺系以外之硬化促進劑並無特殊限定，可使用公知之金屬有機化合物及β-二酮類。 　　金屬有機化合物之例子，可列舉環烷酸銅等之銅化合物、辛酸鈷、環烷酸鈷、氫氧化鈷等之鈷化合物；己酸鋅等之鋅化合物；辛酸錳等之錳化合物等。此等之中尤以環烷酸鈷、辛酸鈷、環烷酸銅為佳。此等之金屬有機化合物，可單獨或組合來使用。 　　β-二酮類之例子，可列舉乙醯基丙酮、乙醯乙酸乙酯、α-乙醯基-γ-丁內酯、N-吡咯啶基乙醯乙醯胺、N,N-二甲基乙醯乙醯胺等。 　　前述金屬有機化合物之摻合量，相對於上述(A)成分與(B)成分之合計100質量份而言，較佳為0.1~5質量份、更佳為0.3~3質量份。金屬有機化合物之摻合量為0.1質量份以上時，容易得到所期望之硬化時間及硬化狀態，乾燥性變得良好。另一方面，金屬有機化合物之摻合量為5質量份以下時，容易得到所期望之可使用時間及貯蔵安定性。[Curing accelerators other than amine-based curing accelerators] The radically polymerizable resin composition of the present invention may contain curing accelerators other than the above-mentioned amine-based curing accelerators. Curing accelerators other than amines are not particularly limited, and known metal organic compounds and β-diketones can be used. Examples of metal organic compounds include copper compounds such as copper naphthenate, cobalt compounds such as cobalt octoate, cobalt naphthenate, and cobalt hydroxide; zinc compounds such as zinc hexanoate; and manganese compounds such as manganese octoate. Among them, cobalt naphthenate, cobalt octoate, and copper naphthenate are particularly preferred. These organometallic compounds can be used alone or in combination. Examples of β-diketones include acetylacetone, ethyl acetate, α-acetyl-γ-butyrolactone, N-pyrrolidinylacetamide, N,N-dimethylacetate Acetylacetamide, etc. The compounding amount of the metal organic compound is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the total of the above-mentioned (A) component and (B) component. When the compounding quantity of a metal organic compound is 0.1 mass part or more, desired hardening time and hardening state are easy to be obtained, and drying property becomes favorable. On the other hand, when the compounding quantity of an organometallic compound is 5 mass parts or less, desired pot life and storage stability are easily obtained.

[光聚合起始劑] 　　以提高硬化性為目的，於本發明之自由基聚合性樹脂組成物中，亦可含有光聚合起始劑。光聚合起始劑例如可列舉光自由基聚合起始劑等。 　　光自由基聚合起始劑，係以促進具有雙鍵之丙烯酸樹脂或單體之聚合，提高硬化性為目的來使用。 　　具體而言，光自由基聚合起始劑，可列舉如苯偶姻烷基醚之苯偶姻醚系；如二苯甲酮、二苯乙二酮、鄰苯甲醯基苯甲酸甲酯等之二苯甲酮系；如苄基二甲基縮酮、2,2-二乙氧基苯乙酮、2-羥基-2-甲基丙醯苯、4-異丙基-2-羥基-2-甲基丙醯苯、1,1-二氯苯乙酮等之苯乙酮系；如2-氯噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮等之噻噸酮系者。 　　相對於(A)自由基反應性樹脂與(B)自由基聚合性不飽和單體之合計100質量份而言，光聚合起始劑能夠以0.1~ 10質量份之範圍添加。[Photopolymerization Initiator] For the purpose of improving curability, the radically polymerizable resin composition of the present invention may contain a photopolymerization initiator. As a photopolymerization initiator, a photoradical polymerization initiator etc. are mentioned, for example. The photo-radical polymerization initiator is used for the purpose of promoting the polymerization of acrylic resins or monomers with double bonds and improving the hardenability. Specifically, photo-radical polymerization initiators include benzoin ethers such as benzoin alkyl ethers; such as benzophenone, benzophenone, methyl o-benzoylbenzoate, etc. The benzophenone series; such as benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropanebenzene, 4-isopropyl-2-hydroxy- Acetophenone series such as 2-methylpropionylbenzene, 1,1-dichloroacetophenone, etc.; such as 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. Thioxanthone series. The photopolymerization initiator can be added in the range of 0.1 to 10 parts by mass relative to 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer.

[界面活性劑] 　　本發明之自由基聚合性樹脂組成物，就使樹脂與水的相容性良好，容易以將水包入樹脂之狀態硬化的觀點而言，亦可含有界面活性劑。 　　界面活性劑可列舉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，及兩性界面活性劑。此等之界面活性劑可單獨、亦可組合2種以上來使用。 　　此等之界面活性劑之中尤以由陰離子性界面活性劑，及非離子性界面活性劑中選出的1種以上為佳。[Surfactant] The radically polymerizable resin composition of the present invention may contain a surfactant from the viewpoint that the resin has good compatibility with water and is easily cured in a state where water is contained in the resin. The surfactant includes anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants may be used alone or in combination of two or more. Among these surfactants, at least one selected from anionic surfactants and nonionic surfactants is preferred.

陰離子性界面活性劑，例如可列舉月桂基硫酸鈉、月桂基硫酸三乙醇胺等之烷基硫酸酯鹽；聚氧乙烯月桂基醚硫酸鈉、聚氧乙烯烷基醚硫酸三乙醇胺等之聚氧乙烯烷基醚硫酸酯鹽；十二烷基苯磺酸、十二烷基苯磺酸鈉、烷基萘磺酸鈉、二烷基磺琥珀酸鈉等之磺酸鹽；硬脂酸鈉皂、油酸鉀皂、蓖麻油鉀皂等之脂肪酸鹽；萘磺酸福馬林縮合物、特殊高分子系等。 　　此等之中尤以磺酸鹽為佳、更佳為二烷基磺琥珀酸鈉、又更佳為二辛基磺琥珀酸鈉。Examples of anionic surfactants include alkyl sulfate ester salts such as sodium lauryl sulfate and triethanolamine lauryl sulfate; polyoxyethylene sulfate such as sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, etc. Alkyl ether sulfate salts; sulfonates of dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, etc.; sodium stearate soap, Fatty acid salts of potassium oleate soap, potassium castor oil soap, etc.; naphthalenesulfonic acid formalin condensate, special polymer system, etc. Among these, sulfonates are particularly preferred, sodium dialkyl sulfosuccinates are more preferred, and dioctyl sodium sulfosuccinates are still more preferred.

非離子性界面活性劑，例如可列舉聚氧月桂基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚等之聚氧乙烯烷基醚；聚氧乙烯二苯乙烯化苯基醚、聚氧乙烯三苄基苯基醚、聚氧乙烯聚氧丙二醇等之聚氧乙烯衍生物；聚氧化烯烷基醚、山梨醇酐單月桂酸酯、山梨醇酐單棕櫚酸酯、山梨醇酐單硬脂酸酯等之山梨醇酐脂肪酸酯；聚氧乙烯山梨醇酐單月桂酸酯、聚氧乙烯山梨醇酐單月桂酸酯、聚氧乙烯山梨醇酐單棕櫚酸酯等之聚氧乙烯山梨醇酐脂肪酸酯；四油酸聚氧乙烯山梨醇等之聚氧乙烯山梨醇脂肪酸酯；甘油單硬脂酸酯、甘油單油酸酯等之甘油脂肪酸酯。Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxylauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene Polyoxyethylene derivatives of distyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, etc.; polyoxyalkylene alkyl ether, sorbitan monolaurate, sorbitan Sorbitan fatty acid esters such as monopalmitate, sorbitan monostearate, etc.; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan Polyoxyethylene sorbitan fatty acid esters such as monopalmitate; polyoxyethylene sorbitan fatty acid esters such as tetraoleic acid polyoxyethylene sorbitol; glycerol monostearate, glycerol monooleate, etc. fatty acid esters.

此等非離子性界面活性劑中，較佳為聚氧乙烯月桂基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚，及聚氧乙烯烷基醚。又，非離子性界面活性劑之HLB(Hydrophile-Lipophil Balance)，較佳為5~15、更佳為6~12。 　　本發明之自由基聚合性樹脂組成物含有界面活性劑時，其含量，相對於(A)自由基聚合性樹脂與(B)自由基聚合性不飽和單體之合計100質量份而言，較佳為0.01~10質量份、更佳為0.05~7質量份、又更佳為0.1~5質量份。Among these nonionic surfactants, preferred are polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene alkyl ether . In addition, the HLB (Hydrophile-Lipophil Balance) of the nonionic surfactant is preferably 5-15, more preferably 6-12. When the radically polymerizable resin composition of the present invention contains a surfactant, the content thereof is more than 100 parts by mass in total of the (A) radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. Preferably it is 0.01-10 mass parts, More preferably, it is 0.05-7 mass parts, More preferably, it is 0.1-5 mass parts.

[界面調整劑] 　　本發明之自由基聚合性樹脂組成物，例如為了提高對濕潤或浸水之被修復部位的滲透性，亦可含有濕潤界面調整劑，作為界面調整劑。 　　濕潤界面調整劑可列舉氟系濕潤界面調整劑及聚矽氧系濕潤界面調整劑等，此等可單獨亦可組合2種以上使用。 　　氟系之濕潤界面調整劑的市售品，可列舉Megafac(註冊商標)F176、Megafac(註冊商標)R08(大日本油墨化學工業(股)製)、PF656、PF6320(OMNOVA公司製)、Troysol S-366(Troy Chemical(股)製)、Fluorad FC430(3M Japan(股)製)、聚矽氧烷聚合物KP-341(信越化學工業(股)製)等。 　　聚矽氧系濕潤分散劑的市售品，可列舉BYK(註冊商標)-322、BYK(註冊商標)-377、BYK(註冊商標)-UV3570、BYK(註冊商標)-330、BYK(註冊商標)-302、BYK(註冊商標)-UV3500、BYK-306(BYK Japan(股)製)、聚矽氧烷聚合物KP-341(信越化學工業(股)製)等。 　　其他濕潤界面調整劑之市售品，可列舉Pelex NBL、Pelex OT-P、Pelex TR(花王(股)製)等。 　　本發明之自由基聚合性樹脂組成物含有界面調整劑時，其含量，相對於(A)自由基聚合性樹脂與(B)自由基聚合性不飽和單體之合計100質量份而言，較佳為0.01~10質量份、更佳為0.1~5質量份為佳。[Interface conditioner] The radical polymerizable resin composition of the present invention may contain a wet interface conditioner as an interface conditioner, for example, in order to improve the permeability of the repaired site that is wet or soaked in water. As the wetting interface modifier, fluorine-based wetting interface modifiers and polysiloxane-based wetting interface modifiers can be cited, and these can be used alone or in combination of two or more. Commercially available fluorine-based wetting interface modifiers include Megafac (registered trademark) F176, Megafac (registered trademark) R08 (manufactured by Dainippon Ink Chemical Co., Ltd.), PF656, PF6320 (manufactured by OMNOVA), Troysol S -366 (manufactured by Troy Chemical Co., Ltd.), Fluorad FC430 (manufactured by 3M Japan Co., Ltd.), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Commercially available polysiloxane-based wetting and dispersing agents include BYK (registered trademark)-322, BYK (registered trademark)-377, BYK (registered trademark)-UV3570, BYK (registered trademark)-330, BYK (registered trademark) )-302, BYK (registered trademark)-UV3500, BYK-306 (manufactured by BYK Japan Co., Ltd.), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Other commercially available wet interface modifiers include Pelex NBL, Pelex OT-P, and Pelex TR (manufactured by Kao Corporation). When the radically polymerizable resin composition of the present invention contains an interface modifier, the content thereof is higher than 100 parts by mass in total of the (A) radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. Preferably it is 0.01-10 mass parts, More preferably, it is 0.1-5 mass parts.

[搖變劑] 　　本發明之自由基聚合性樹脂組成物，以用於確保於垂直面或天花板面之作業性的黏度調整等為目的，亦可含有搖變劑。 　　搖變劑可列舉無機系搖變劑及有機系搖變劑，有機系搖變劑可列舉氫化蓖麻油系、醯胺系、氧化聚乙烯系、植物油聚合油系、界面活性劑系，及合併使用此等之複合系，具體而言，可列舉DISPARLON(註冊商標)6900-20X(楠本化成(股))等。 　　又，無機系搖變劑可列舉二氧化矽或皂土系，疏水性者可列舉Reolosil(註冊商標)PM-20L((股)Tokuyama製之氣相法二氧化矽)、Aerosil(註冊商標)AEROSIL R-106 (日本Aerosil(股))等，親水性者可列舉Aerosil(註冊商標) AEROSIL-200(日本Aerosil(股))等。就更提高搖變性之觀點而言，亦可適合地使用於親水性之燒成二氧化矽中，添加有搖變性改質劑BYK(註冊商標)-R605或BYK(註冊商標)-R606(BYK Japan(股)製)者。 　　本發明之自由基聚合性樹脂組成物含有搖變劑時，其含量，相對於(A)自由基聚合性樹脂與(B)自由基聚合性不飽和單體之合計100質量份而言，較佳為0.01~10質量份、更佳為0.1~5質量份為佳。[Thixotrope] The radically polymerizable resin composition of the present invention may contain a thixotrope for the purpose of adjusting the viscosity, etc. to ensure workability on a vertical surface or a ceiling surface. Examples of thixotropic agents include inorganic thixotropic agents and organic thixotropic agents. Examples of organic thixotropic agents include hydrogenated castor oil series, amide series, oxidized polyethylene series, vegetable oil polymerized oil series, surfactant series, and combinations thereof. Using these composite systems, specifically, DISPARLON (registered trademark) 6900-20X (Kusumoto Chemical Co., Ltd.) and the like can be mentioned. In addition, examples of inorganic thixotropic agents include silica or bentonite, and examples of hydrophobic agents include Reolosil (registered trademark) PM-20L (fumed silica manufactured by Tokuyama), Aerosil (registered trademark) Aerosil (registered trademark), AEROSIL-200 (Japan Aerosil, Inc.), etc. are exemplified as hydrophilic ones. From the viewpoint of improving thixotropy, it can also be suitably used in hydrophilic sintered silica, adding thixotropy modifier BYK (registered trademark)-R605 or BYK (registered trademark)-R606 (BYK Japan (stock) system). When the radically polymerizable resin composition of the present invention contains a thixotropic agent, the content thereof is higher than 100 parts by mass in total of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. Preferably it is 0.01-10 mass parts, More preferably, it is 0.1-5 mass parts.

[濕潤分散劑] 　　本發明之自由基聚合性樹脂組成物，以填充劑混合時之高填充、黏度降低、沈降防止等為目的，亦可含有濕潤分散劑。此等可單獨、亦可組合2種以上來使用。 　　濕潤分散劑之市售品可列舉BYK-W909、BYK-W985、BYK-W966、BYK-W980、BYK-W969、BYK-W996、BYK-W9010、BYK-W940等。 　　本發明之自由基聚合性樹脂組成物含有濕潤分散劑時，其含量，相對於(A)自由基聚合性樹脂與(B)自由基聚合性不飽和單體之合計100質量份而言，較佳為0.1~5.0質量份、更佳為0.3~3.0質量份、又更佳為0.5~2.0質量份為佳。[Wetting and dispersing agent] The radically polymerizable resin composition of the present invention may contain a wetting and dispersing agent for the purpose of high filling, viscosity reduction, and sedimentation prevention when the filler is mixed. These may be used alone or in combination of two or more. Commercially available wetting dispersants include BYK-W909, BYK-W985, BYK-W966, BYK-W980, BYK-W969, BYK-W996, BYK-W9010, BYK-W940, etc. When the radically polymerizable resin composition of the present invention contains a wetting and dispersing agent, the content thereof is more than 100 parts by mass in total of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. Preferably it is 0.1-5.0 mass parts, More preferably, it is 0.3-3.0 mass parts, More preferably, it is 0.5-2.0 mass parts.

[硬化延遲劑] 　　本發明之自由基聚合性樹脂組成物，以硬化時間之調整之目的，亦可含有硬化延遲劑。硬化延遲劑可列舉自由基系硬化延遲劑，例如可列舉2,2,6,6-四甲基哌啶1-氧化物 自由基(TEMPO)、4-羥基-2,2,6,6-四甲基哌啶1-氧化物 自由基(4H-TEMPO)、4-側氧基-2,2,6,6-四甲基哌啶1-氧化物 自由基(4-Oxo-TEMPO)等之TEMPO衍生物。此等之中，就成本面、操作容易性之觀點而言，尤以4-羥基-2,2,6,6-四甲基哌啶1-氧化物 自由基(4H-TEMPO)為佳。 　　本發明之自由基聚合性樹脂組成物含有聚合抑制劑、硬化延遲劑時，相對於(A)自由基聚合性樹脂與(B)自由基聚合性不飽和單體之合計100質量份而言，其量較佳為各0.0001~10質量份、更佳為各0.001~10質量份。[Curing retarder] The radically polymerizable resin composition of the present invention may contain a curing retarder for the purpose of adjusting the curing time. Examples of the curing retarder include radical-based curing retarders, for example, 2,2,6,6-tetramethylpiperidine 1-oxide radical (TEMPO), 4-hydroxy-2,2,6,6- Tetramethylpiperidine 1-oxide radical (4H-TEMPO), 4-oxy-2,2,6,6-tetramethylpiperidine 1-oxide radical (4-Oxo-TEMPO), etc. TEMPO derivatives. Among these, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxide radical (4H-TEMPO) is particularly preferable in terms of cost and ease of handling. When the radically polymerizable resin composition of the present invention contains a polymerization inhibitor and a curing retarder, the total amount of (A) the radically polymerizable resin and (B) 100 parts by mass of the radically polymerizable unsaturated monomer in total is The amount is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 10 parts by mass.

[消泡劑] 　　本發明之自由基聚合性樹脂組成物，以改善成形時產生氣泡、成形品氣泡殘留為目的，亦可含有消泡劑。消泡劑可列舉聚矽氧系消泡劑、聚合物系消泡劑等。 　　消泡劑之使用量，相對於(A)自由基聚合性樹脂與(B)自由基聚合性不飽和單體之合計100質量份而言，較佳為0.01~5質量份之範圍。更佳為0.1~1質量份。[Defoamer] The radical polymerizable resin composition of the present invention may contain a defoamer for the purpose of improving the generation of air bubbles during molding and the remaining of air bubbles in the molded product. As the defoaming agent, a polysiloxane-based defoaming agent, a polymer-based defoaming agent, and the like are exemplified. The amount of the defoamer to be used is preferably in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of the total of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. More preferably, it is 0.1-1 mass part.

[偶合劑] 　　本發明之自由基聚合性樹脂組成物，以提高對修復對象物之基材的密合性等為目的，亦可含有偶合劑。偶合劑可列舉公知之矽烷系偶合劑、鈦酸酯系偶合劑、鋁系偶合劑等。 　　如此之偶合劑，例如可列舉R5 -Si(OR6 )3 表示之矽烷偶合劑。再者，R5 例如可列舉胺基丙基、縮水甘油氧基、(甲基)丙烯醯氧基、N-苯基胺基丙基、巰基、乙烯基等，R6 例如可列舉甲基、乙基等。 　　本發明之自由基聚合性樹脂組成物含有偶合劑時，其含量，相對於(A)自由基聚合性樹脂與(B)自由基聚合性不飽和單體之合計100質量份而言，較佳為0.001~10質量份、更佳為0.01~5質量份。[Coupling Agent] The radically polymerizable resin composition of the present invention may contain a coupling agent for the purpose of improving the adhesion to the base material of the repair object. The coupling agent includes known silane-based coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and the like. Such a coupling agent includes, for example, a silane coupling agent represented by R 5 -Si(OR 6 ) 3 . Furthermore, R 5 includes, for example, aminopropyl, glycidyloxy, (meth)acryloyloxy, N-phenylaminopropyl, mercapto, vinyl, and the like, and R 6 includes, for example, methyl, Ethyl etc. When the radically polymerizable resin composition of the present invention contains a coupling agent, the content of the coupling agent is preferably 100 parts by mass in total of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. It is 0.001-10 mass parts, More preferably, it is 0.01-5 mass parts.

[光安定劑] 　　本發明之自由基聚合性樹脂組成物，以提高成形品之長期耐久性為目的，亦可使用光安定劑。光安定劑可列舉紫外線吸收劑或受阻胺系光安定劑。此等可單獨亦可組合2種以上使用。具體而言，紫外線吸收劑可列舉苯并***系、三嗪系、二苯甲酮系、氰基丙烯酸酯系、水楊酸酯系等，受阻胺系光安定劑可列舉N-H型、N-CH3 型、N-O烷基型等。 　　光安定劑之使用量，相對於(A)自由基聚合性樹脂與(B)自由基聚合性不飽和單體之合計100質量份而言，較佳為0.01~5質量份之範圍、更佳為0.05~2質量份。[Light stabilizer] In the radically polymerizable resin composition of the present invention, a light stabilizer may also be used for the purpose of improving the long-term durability of the molded article. As the light stabilizer, an ultraviolet absorber or a hindered amine-based light stabilizer is exemplified. These may be used alone or in combination of two or more. Specifically, examples of ultraviolet absorbers include benzotriazole-based, triazine-based, benzophenone-based, cyanoacrylate-based, and salicylate-based light stabilizers, and examples of hindered amine-based light stabilizers include NH-type, N-type -CH 3 type, NO alkyl type, etc. The usage-amount of the photostabilizer is preferably in the range of 0.01 to 5 parts by mass, more preferably 100 parts by mass in total of the (A) radically polymerizable resin and (B) the radically polymerizable unsaturated monomer It is 0.05-2 mass parts.

[蠟] 　　本發明之自由基聚合性樹脂組成物，以提高表面乾燥性為目的，亦可含有蠟。蠟可單獨或合併使用石蠟類、極性蠟類等，可使用各種熔點之公知物。 　　極性蠟類可列舉構造中一併具備極性基及非極性基者。具體而言，可列舉NPS-8070、NPS-9125(日本精蠟公司製)、Emanon 3199、3299(花王公司製)、BYK(註冊商標)-S740、BYK(註冊商標)-S750N、BYK(註冊商標)-S760、BYK(註冊商標)-S780、BYK(註冊商標)-S781、BYK(註冊商標)-S782等。 　　相對於(A)自由基聚合性樹脂與(B)自由基聚合性不飽和單體之合計100質量份而言，蠟較佳含有0.05~4質量份、更佳含有0.1~2.0質量份。[Wax] The radically polymerizable resin composition of the present invention may contain wax for the purpose of improving surface drying properties. As the wax, paraffin waxes, polar waxes, etc. can be used alone or in combination, and known ones with various melting points can be used. Polar waxes include those with both polar groups and non-polar groups in their structure. Specifically, NPS-8070, NPS-9125 (manufactured by Nippon Seiki Co., Ltd.), Emanon 3199, 3299 (manufactured by Kao Corporation), BYK (registered trademark)-S740, BYK (registered trademark)-S750N, BYK (registered trademark) trademark)-S760, BYK (registered trademark)-S780, BYK (registered trademark)-S781, BYK (registered trademark)-S782, etc. The wax is preferably contained in an amount of 0.05 to 4 parts by mass, more preferably 0.1 to 2.0 parts by mass, relative to 100 parts by mass of the total of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer.

[難燃劑] 　　本發明之自由基聚合性樹脂組成物，亦可含有難燃劑。難燃劑可單獨或合併使用溴系難燃劑、氯系難燃劑、磷系難燃劑、無機系難燃劑、膨脹(intumescent)系難燃劑、聚矽氧系難燃劑等，可使用公知者。 　　又，溴系難燃劑等之鹵素系難燃劑，以進一步提高難燃性為目的，可與三氧化銻合併使用。 　　難燃劑之添加量，雖依難燃劑之系統或種類而異，但相對於(A)自由基聚合性樹脂與(B)自由基聚合性不飽和單體之合計100質量份而言，較佳含有1~100質量份。[Flame retardant] The radically polymerizable resin composition of the present invention may contain a flame retardant. The flame retardants can be used alone or in combination with bromine-based flame retardants, chlorine-based flame retardants, phosphorus-based flame retardants, inorganic flame retardants, intumescent flame retardants, polysiloxane-based flame retardants, etc. Well-known ones can be used. In addition, halogen-based flame retardants such as brominated flame retardants can be used in combination with antimony trioxide for the purpose of further improving the flame retardancy. The amount of the flame retardant added varies depending on the system or type of the flame retardant, but is based on 100 parts by mass of the total of (A) the radical polymerizable resin and (B) the radical polymerizable unsaturated monomer. It is preferable to contain 1-100 mass parts.

[可塑劑] 　　本發明之樹脂組成物，以黏度調整、硬化物之柔軟性調整為目的，亦可含有可塑劑。可塑劑可單獨或合併使用環氧類、聚酯類系、鄰苯二甲酸酯類系、己二酸酯類系、偏苯三甲酸酯類系、磷酸酯類系、檸檬酸酯類系、癸二酸酯類系、壬二酸酯類系、馬來酸酯類系、苯甲酸酯類系等，可使用公知者。 　　可塑劑之添加量雖依其種類而異，但相對於(A)自由基聚合性樹脂與(B)自由基聚合性不飽和單體之合計100質量份而言，較佳含有0.01~20質量份。更佳含有0.1~10質量份。[Plasticizer] The resin composition of the present invention may contain a plasticizer for the purpose of adjusting the viscosity and adjusting the flexibility of the cured product. Plasticizers can be used alone or in combination with epoxy, polyester, phthalate, adipate, trimellitic, phosphate, citrate, As the sebacate-based, azelaic-based, maleic-based, benzoic-based, etc., known ones can be used. Although the amount of plasticizer added varies depending on the type, it is preferable to contain 0.01 to 20 parts by mass relative to 100 parts by mass of the total of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer share. More preferably, it contains 0.1-10 mass parts.

本發明之自由基聚合性樹脂組成物中，(A)成分、(B)成分、(C)成分，及(D)成分之含量的總量，較佳為30~100質量%、更佳為60~100質量%、又更佳為90~100質量%。 　　又，本發明之自由基聚合性樹脂組成物含有(E)硬化劑時，本發明之自由基聚合性樹脂組成物中，(A)成分、(B)成分、(C)成分、(D)成分及(E)硬化劑之含量的總量，較佳為30~100質量%、更佳為60~100質量%、又更佳為90~100質量%。In the radical polymerizable resin composition of the present invention, the total content of the components (A), (B), (C), and (D) is preferably 30 to 100% by mass, more preferably 60 to 100 mass %, more preferably 90 to 100 mass %. Moreover, when the radical polymerizable resin composition of this invention contains (E) hardening agent, in the radical polymerizable resin composition of this invention, (A) component, (B) component, (C) component, (D) 30-100 mass % is preferable, 60-100 mass % is more preferable, and 90-100 mass % is still more preferable as the total amount of content of a component and (E) hardening|curing agent.

＜自由基聚合性樹脂組成物之黏度＞ 　　本發明之自由基聚合性樹脂組成物之黏度，就對無機構造物之龜裂的注入容易性、對填充材料等之混合容易性的觀點而言，較佳為10~1000mPa･s/25℃、更佳為30~ 500mPa･s/25℃、又更佳為50~400mPa･s/25℃。此處，黏度之測定方法，係如實施例所記載。<Viscosity of the radically polymerizable resin composition> The viscosity of the radically polymerizable resin composition of the present invention is, from the viewpoints of the ease of injection into cracks in the inorganic structure and the ease of mixing with fillers and the like, It is preferably 10 to 1000 mPa･s/25°C, more preferably 30 to 500 mPa･s/25°C, still more preferably 50 to 400 mPa･s/25°C. Here, the method for measuring the viscosity is as described in the Examples.

＜自由基聚合性樹脂組成物之製造方法＞ 　　本發明之自由基聚合性樹脂組成物之製造方法，各成分的混合順序無特別限定，但就用以效率良好地得到均勻混合物的作業性之觀點，又，就作為自由基聚合性組成物之黏度調整等，將組成物調整為目標物性範圍時的作業性之觀點而言，較佳於合成(A)成分後，添加(B)成分之一部分並混合，使(A)成分低黏度化後，添加剩餘的(B)成分與其他成分並混合。或者，較佳於(A)成分合成時，使用(B)成分之一部分作為稀釋劑，得到(A)成分與一部分(B)成分之混合物後，添加剩餘的(B)成分與其他成分並混合。低黏度化時之(A)成分與一部分(B)成分的混合比例並無特殊限定，較佳為以質量比計95：5~20：80、更佳為85：15~ 30：70。 　　(A)成分與一部分(B)成分之混合物的黏度，較佳為50~4000mPa･s、更佳為80~3000mPa･s、又更佳為100~ 2000mPa･s。黏度之測定方法，係如實施例所記載。若預先調整為上述範圍之黏度，則混合剩餘成分成為本發明之自由基聚合性樹脂組成物時，能夠以短時間均勻地混合。<Method for producing a radically polymerizable resin composition> In the method for producing a radically polymerizable resin composition of the present invention, the mixing order of each component is not particularly limited, but from the viewpoint of workability for efficiently obtaining a homogeneous mixture Also, from the viewpoint of workability when the composition is adjusted to the target physical property range, such as viscosity adjustment as a radically polymerizable composition, it is preferable to add a part of the (B) component after synthesizing the (A) component. After mixing and reducing the viscosity of (A) component, the remaining (B) component and other components are added and mixed. Alternatively, it is preferable to use a part of (B) component as a diluent when synthesizing the (A) component to obtain a mixture of the (A) component and a part of the (B) component, and then add and mix the remaining (B) component and other components. . The mixing ratio of (A) component and a part of (B) component at the time of lowering the viscosity is not particularly limited, but is preferably 95:5 to 20:80 in terms of mass ratio, more preferably 85:15 to 30:70. The viscosity of the mixture of component (A) and a part of component (B) is preferably 50~4000mPa･s, more preferably 80~3000mPa･s, and still more preferably 100~2000mPa･s. The measurement method of viscosity is as described in the examples. When the viscosity of the above-mentioned range is adjusted in advance, when the remaining components are mixed to form the radically polymerizable resin composition of the present invention, it can be uniformly mixed in a short time.

[構造物修復材料] 　　本發明之自由基聚合性樹脂組成物，可使用作為含有該自由基聚合性樹脂組成物之構造物修復材料。 　　構造物例如可列舉混凝土、瀝青混凝土、砂漿、金屬等之無機構造物或木材。特佳可使用作為高速道路或鐵道等之版式軌道之構造物修復材料。[Structural Repair Material] The radically polymerizable resin composition of the present invention can be used as a structural repair material containing the radically polymerizable resin composition. Examples of the structure include inorganic structures such as concrete, asphalt concrete, mortar, and metals, and wood. Tejia can be used as a structural repair material for layout tracks such as highways or railways.

＜填充材料(F)＞ 　　本發明之構造物修復材料，可使用本發明之自由基聚合性樹脂組成物作為構造物修復材料，可於本發明之自由基聚合性樹脂組成物中含有填充材料(F)，來作為構造物修復材料。填充材料(F)並無特殊限定，例如可列舉無機填充材料，及有機填充材料。 　　無機填充材料可使用水泥、生石灰、河礫、川砂、海礫、海砂、山礫、碎石、碎砂、矽砂等之以二氧化矽為主成分的砂、碳酸鈣、陶瓷、玻璃屑等之人工骨材、滑石、沸石、活性碳等之公知者，但就流動性、材料成本節減、材料獲得的觀點而言，較佳為矽砂、碳酸鈣、滑石、發煙二氧化矽之組合。矽砂可使用天然矽砂、蛙目矽砂、人造矽砂等。矽砂之尺寸，可使用3號~8號左右者。碳酸鈣可使用合成碳酸鈣、輕質碳酸鈣、重質碳酸鈣。碳酸鈣之平均粒子徑並無特殊限定，可使用一般所使用的範圍者。又，就賦予難燃性之觀點而言，可使用氫氧化鋁。又，就著色之觀點而言，亦可使用氧化鈦或氧化鐵等之著色劑或無機顏料，進一步地，亦可使用分子篩。無機填充材料之粒度較佳為1nm~5000μm、更佳為10nm~3000μm。無機填充材料之粒度於上述範圍內時，可得到良好的作業性或物性。 　　有機填充材料，亦可使用醯胺系蠟、吸水聚合物等之有機系填充材料。<Filling material (F)> In the structural repair material of the present invention, the radical polymerizable resin composition of the present invention may be used as the structural repair material, and the radical polymerizable resin composition of the present invention may contain a filler ( F), as a structural repair material. The filler (F) is not particularly limited, and examples thereof include inorganic fillers and organic fillers. Inorganic filler materials can be sand, calcium carbonate, ceramics, glass chips, such as cement, quicklime, river gravel, river sand, sea gravel, sea sand, mountain gravel, crushed stone, crushed sand, silica sand, etc. Such as artificial aggregates, talc, zeolite, activated carbon, etc. are known, but from the viewpoints of fluidity, material cost reduction, and material availability, silica sand, calcium carbonate, talc, and fumed silica are preferred. combination. Silica sand can use natural silica sand, frog mesh silica sand, artificial silica sand, etc. The size of silica sand can be about 3 to 8. As the calcium carbonate, synthetic calcium carbonate, light calcium carbonate, and heavy calcium carbonate can be used. The average particle size of calcium carbonate is not particularly limited, and a generally used range can be used. Moreover, from the viewpoint of imparting flame retardancy, aluminum hydroxide can be used. Moreover, from the viewpoint of coloring, a coloring agent such as titanium oxide or iron oxide, or an inorganic pigment can also be used, and furthermore, a molecular sieve can also be used. The particle size of the inorganic filler is preferably 1 nm to 5000 μm, more preferably 10 nm to 3000 μm. When the particle size of the inorganic filler is within the above range, good workability and physical properties can be obtained. As the organic filler, organic fillers such as amide waxes and water-absorbing polymers can also be used.

又，前述填充材料(F)亦可使用纖維。纖維的具體例子，可列舉玻璃纖維、碳纖維、鹼性硫酸鎂纖維、維尼綸纖維、耐綸纖維、聚芳醯胺纖維、聚丙烯纖維、丙烯酸纖維、聚對苯二甲酸乙二酯纖維等之聚酯纖維、纖維素纖維、鋼纖維等之金屬纖維、氧化鋁纖維等之陶瓷纖維、玄武岩纖維等之天然纖維等。此等之纖維，較佳例如將由平織、緞織、不織布、氈狀物(mat)、粗紗(roving)、切股、片狀物、編織物、編帶物，及此等之複合構造物等中選出的纖維構造體，以二軸網目、三軸網目之形態使用。例如，可於前述纖維構造體中含浸自由基聚合性組成物，依情況進行預聚合而預浸物化來使用。 　　網目例如使用二軸網目、三軸網目。二軸網目之正方形之一邊的長度(網目尺寸)及三軸網目之正三角形之一邊的長度(網目尺寸)，較佳各為5mm以上、更佳為10~ 20mm。藉由使用二軸網目或三軸網目，可得到輕量且經濟性、施工性、耐久性優良的構造物補強材料。 　　此等之纖維，較佳於補強構造物等時使用。 　　構造物補強等之用途中，於纖維當中，尤以強度、成本優良之玻璃纖維、纖維素纖維等，就可自外側以目視檢查基底之劣化狀態的觀點較佳。又，就強度、輕量化優良的觀點，碳纖維亦佳。前述填充材料(F)可1種單獨使用、亦可合併使用2種以上。Moreover, a fiber can also be used for the said filler (F). Specific examples of fibers include glass fibers, carbon fibers, basic magnesium sulfate fibers, vinylon fibers, nylon fibers, polyaramid fibers, polypropylene fibers, acrylic fibers, polyethylene terephthalate fibers, and the like. Polyester fiber, cellulose fiber, metal fiber such as steel fiber, ceramic fiber such as alumina fiber, natural fiber such as basalt fiber, etc. These fibers are preferably made of, for example, plain weave, satin weave, non-woven fabric, mat, roving, strand, sheet, braid, braid, and composite structures thereof, etc. The selected fiber structure is used in the form of biaxial mesh and triaxial mesh. For example, the above-mentioned fiber structure can be impregnated with a radically polymerizable composition, prepolymerized in some cases, and used as a prepreg. For the mesh, for example, two-axis mesh and three-axis mesh are used. The length (mesh size) of one side of the square of the two-axis mesh and the length (mesh size) of one side of the equilateral triangle of the three-axis mesh are preferably 5 mm or more, more preferably 10-20 mm. By using a biaxial mesh or a triaxial mesh, it is possible to obtain a structural reinforcement material that is lightweight and excellent in economy, workability, and durability. These fibers are preferably used for reinforcing structures and the like. In applications such as structural reinforcement, among fibers, glass fibers, cellulose fibers, etc., which are excellent in strength and cost, are preferable in that the deterioration state of the base can be visually inspected from the outside. Moreover, carbon fiber is also preferable from the viewpoint of being excellent in strength and weight reduction. The said filler (F) may be used individually by 1 type, and may use 2 or more types together.

本發明之構造物修復材料含有填充材料(F)時，其摻合量，相對於上述(A)成分與(B)成分之合計100質量份而言，較佳為1~700質量份、更佳為10~600質量份、又更佳為50~500質量份。使用纖維作為填充材料(F)時，其摻合量，相對於(A)成分與(B)成分之合計100質量份而言，較佳為5~400質量份、更佳為15~300質量份、又更佳為30~250質量份。填充材料之摻合比例若為上述範圍內，則硬化性或作業性良好而較佳。When the structural repair material of the present invention contains the filler (F), the blending amount thereof is preferably 1 to 700 parts by mass, more preferably 100 parts by mass in total of the above-mentioned (A) component and (B) component. Preferably it is 10-600 mass parts, More preferably, it is 50-500 mass parts. When fiber is used as the filler (F), the blending amount is preferably 5 to 400 parts by mass, more preferably 15 to 300 parts by mass with respect to 100 parts by mass of the total of (A) component and (B) component parts, and more preferably 30 to 250 parts by mass. If the blending ratio of the filler is within the above-mentioned range, the curability and workability are good, which is preferable.

構造物之修復方法並無特殊限定，例如可藉由將本發明之構造物修復材料，塗佈於混凝土、瀝青混凝土、砂漿、木材、金屬等之修復部位並乾燥、硬化來進行。構造物修復材料之塗佈方法並無特殊限定，例如可應用以浸漬之塗佈方法、以噴霧之塗佈方法、以輥之塗佈方法、使用刷子、刷毛或抹刀等之器具的塗佈方法等。 　　構造物修復材料之塗佈量並無特殊限定，係考慮修復部位之大小、構造物修復材料之密合性、該構造物修復材料之硬化體的強度等來適當調整。 　　塗佈構造物修復材料後之乾燥方法並無特殊限定，可使用自然乾燥之方法，或於構造物修復材料之硬化體的特性不會劣化的範圍內加熱之方法。 　　又，亦可藉由將本發明之構造物修復材料直接注入於構造物之龜裂產生部位，並乾燥、硬化來修復。 [實施例]The repairing method of the structure is not particularly limited. For example, the repairing material for the structure of the present invention can be applied to the repaired part of concrete, asphalt concrete, mortar, wood, metal, etc., and then dried and hardened. The coating method of the structure repair material is not particularly limited. For example, a coating method by dipping, a coating method by spraying, a coating method by a roller, and a coating method using a brush, bristles, or spatula can be applied. method etc. The coating amount of the structural repair material is not particularly limited, and it is appropriately adjusted in consideration of the size of the repaired part, the tightness of the structural repair material, and the strength of the hardened body of the structural repair material. The drying method after applying the structure repair material is not particularly limited, and a natural drying method or a method of heating within the range where the properties of the hardened body of the structure repair material will not deteriorate can be used. In addition, the structure repairing material of the present invention can also be repaired by directly injecting the structure repairing material into the cracked part of the structure, drying and hardening. [Example]

以下，基於實施例來說明本發明，但本發明不受實施例限制。Hereinafter, the present invention will be described based on examples, but the present invention is not limited by the examples.

＜合成例＞ 　　如後所述，使用以下之原料，合成(A)自由基聚合性樹脂之胺基甲酸酯甲基丙烯酸酯樹脂(UM1)，接著混合作為(B)自由基聚合性不飽和單體之甲基丙烯酸甲酯(三菱縲縈(股)製、製品名：Acryester M)，得到(A)成分與(B)成分之混合物。<Synthesis example> As described later, the following raw materials were used to synthesize (A) a urethane methacrylate resin (UM1) of a radically polymerizable resin, followed by mixing as (B) a radically polymerizable unsaturated Monomer methyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., product name: Acryester M), a mixture of (A) component and (B) component was obtained.

胺基甲酸酯甲基丙烯酸酯樹脂(UM1)之原料如以下所示。 (多元醇) 　　聚丙二醇1(重量平均分子量1000)、三井化學(股)製、製品名：Actcol D-1000 　　聚丙二醇2(重量平均分子量2000)、三井化學(股)製、製品名：Actcol D-2000 (多元異氰酸酯) 　　二苯基甲烷二異氰酸酯 (含有羥基之(甲基)丙烯酸酯) 　　甲基丙烯酸2-羥基丙酯 　　接著，具體說明胺基甲酸酯甲基丙烯酸酯樹脂(UM1)之合成例。The raw materials of the urethane methacrylate resin (UM1) are shown below. (Polyol) Polypropylene glycol 1 (weight average molecular weight 1000), manufactured by Mitsui Chemicals Co., Ltd., product name: Actcol D-1000 Polypropylene glycol 2 (weight average molecular weight 2000), manufactured by Mitsui Chemicals Co., Ltd., product name: Actcol D -2000 (polyisocyanate) Diphenylmethane diisocyanate ((meth)acrylate containing hydroxyl group) 2-hydroxypropyl methacrylate Next, the synthesis of urethane methacrylate resin (UM1) will be described in detail example.

(合成例1) 　　於具備攪拌器、回流冷卻管、氣體導入管及溫度計之3L的4口燒瓶中，給入二苯基甲烷二異氰酸酯：500g(2.0 mol)、Actcol D-1000(三井化學(股)製聚丙二醇1：重量平均分子量1000)：100g(0.1mol)、Actcol D-2000(三井化學(股)製聚丙二醇2：重量平均分子量2000)：1800g (0.9 mol)，及二月桂酸二丁基錫：0.2g，於60℃攪拌4小時使其反應。接著，對該反應物，花費2小時滴下甲基丙烯酸2-羥基丙酯：288g(2.0mol)同時攪拌，滴下結束後攪拌5小時使其反應，得到胺基甲酸酯甲基丙烯酸酯樹脂(UM1)。所得胺基甲酸酯甲基丙烯酸酯樹脂(UM1)以下述測定方法所得的重量平均分子量為9055。 　　接著，對該胺基甲酸酯甲基丙烯酸酯樹脂(UM1)添加甲基丙烯酸甲酯：1035g，得到(A)成分與(B)成分之混合物。又，以下述測定方法所得的混合物於25℃之黏度為300mPa･s、液體比重為1.02。(Synthesis Example 1) Into a 3-L 4-neck flask equipped with a stirrer, a reflux cooling tube, a gas introduction tube, and a thermometer, diphenylmethane diisocyanate: 500 g (2.0 mol), Actcol D-1000 (Mitsui Chemicals (Mitsui Chemicals) Co., Ltd.) polypropylene glycol 1: weight average molecular weight 1000): 100 g (0.1 mol), Actcol D-2000 (Mitsui Chemicals Co., Ltd. polypropylene glycol 2: weight average molecular weight 2000): 1800 g (0.9 mol), and dilauric acid Dibutyltin: 0.2 g, the mixture was stirred at 60°C for 4 hours to react. Next, to this reactant, 2-hydroxypropyl methacrylate: 288 g (2.0 mol) was dropped over 2 hours while stirring, and after the dropping was completed, the reaction was stirred for 5 hours to obtain a urethane methacrylate resin ( UM1). The weight average molecular weight of the obtained urethane methacrylate resin (UM1) obtained by the following measurement method was 9055. Next, methyl methacrylate: 1035 g was added to the urethane methacrylate resin (UM1) to obtain a mixture of (A) component and (B) component. In addition, the viscosity at 25 degreeC of the mixture obtained by the following measurement method was 300 mPa·s, and the liquid specific gravity was 1.02.

＜重量平均分子量之測定＞ 　　使用凝膠滲透層析(昭和電工(股)製Shodex GPC-101)。重量平均分子量係以下述條件於常溫(23℃)測定，以聚苯乙烯換算來算出。 (測定條件) 　　管柱：昭和電工(股)製LF-804、2支 　　管柱溫度：40℃ 　　試樣：被測定物之0.4質量%四氫呋喃溶液 　　流量：1ml/分鐘 　　溶離液：四氫呋喃<Measurement of weight average molecular weight> Gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko Co., Ltd.) was used. The weight average molecular weight is measured at normal temperature (23° C.) under the following conditions, and is calculated in terms of polystyrene. (Measurement conditions) Column: LF-804 manufactured by Showa Denko Co., Ltd., 2 pieces Column temperature: 40°C Sample: 0.4 mass % tetrahydrofuran solution of the object to be measured Flow rate: 1 ml/min Elution solution: tetrahydrofuran

＜黏度之測定＞ 　　使用東機產業(股)製RE-85型黏度計、錐板型、錐型轉子1˚34’×R24，以旋轉數100rpm測定25℃環境下之黏度。<Measurement of Viscosity> Viscosities at 25°C were measured at 100 rpm using a RE-85 viscometer manufactured by Toki Sangyo Co., Ltd.

＜液體比重之測定＞ 　　根據JIS K 7112-1999 之附屬書2「塑膠-液狀樹脂-水中取代法」，使用Alfa Mirage(股)製電子比重計MD-200S，測定於23℃之液體比重。<Determination of liquid specific gravity> According to the appendix 2 of JIS K 7112-1999 "Plastic-Liquid Resin-Water Substitution Method", the electronic hydrometer MD-200S manufactured by Alfa Mirage Co., Ltd. was used to measure the liquid specific gravity at 23°C.

實施例1~17 　　作為原料，係將合成例1中得到之混合物、依需要之前述(B)自由基聚合性不飽和單體，與以下之(C)胺系硬化促進劑、(D)多官能硫醇化合物、(E)硬化劑，作為自由基聚合性樹脂組成物之原料。 　　(C)胺系硬化促進劑 　　N,N-雙(2-羥基丙基)-p-甲苯胺、和光純藥工業(股)製、製品名：Accelerator A 　　(D)多官能硫醇化合物 　　(1)季戊四醇肆(3-巰基丁酸酯)、4官能2級硫醇、昭和電工(股)製、製品名：Karenz MT PE1 　　(2)三羥甲基丙烷-參(3-巰基丁酸酯)3官能2級硫醇、昭和電工(股)製、製品名：TPMB 　　(3)1,4-雙(3-巰基丁醯氧基)丁烷、2官能2級硫醇、昭和電工(股)製、製品名：Karenz MT BD1 　　(4)季戊四醇肆(3-巰基丙酸酯)、4官能1級硫醇、SC有機化學(股)製、製品名：PEMP 　　(5)三羥甲基丙烷參硫代丙酸酯、3官能1級硫醇、淀化學(股)製、製品名：TMTP 　　(E)硬化劑 　　二苯甲醯基過氧化物、化藥Akzo(股)製、製品名：Perkadox CH-50LExamples 1 to 17 As raw materials, the mixture obtained in Synthesis Example 1, the aforementioned (B) radically polymerizable unsaturated monomer as required, and the following (C) amine-based hardening accelerators and (D) polyamides were used. Functional thiol compound and (E) hardener are used as raw materials for radically polymerizable resin compositions. (C) Amine-based hardening accelerator N,N-bis(2-hydroxypropyl)-p-toluidine, manufactured by Wako Pure Chemical Industries, Ltd., product name: Accelerator A (D) Polyfunctional thiol compound (1) ) Pentaerythritol (3-mercaptobutyrate), tetrafunctional 2-level mercaptan, manufactured by Showa Denko Co., Ltd., product name: Karenz MT PE1 (2) Trimethylolpropane-sam (3-mercaptobutyrate) Trifunctional secondary thiol, manufactured by Showa Denko Co., Ltd., product name: TPMB (3) 1,4-bis(3-mercaptobutanoyloxy)butane, bifunctional secondary thiol, Showa Denko Co., Ltd. Manufacturer, product name: Karenz MT BD1 (4) Pentaerythritol (3-mercaptopropionate), 4-functional first-class mercaptan, manufactured by SC Organic Chemical Co., Ltd., product name: PEMP (5) Trimethylolpropane ginseng Thiopropionate, trifunctional first-order mercaptan, manufactured by Yodo Chemical Co., Ltd., product name: TMTP (E) Hardener dibenzoyl peroxide, manufactured by Akzo Chemical Co., Ltd., product name: Perkadox CH-50L

對前述(A)成分與(B)成分之混合物，添加(B)自由基聚合性不飽和單體，以(A)成分/(B)成分之質量比成為65/35的方式，得到由(A)成分及(B)成分所構成之預備試樣。接著，對該預備試樣100質量份，亦即(A)成分及(B)成分之合計100質量份，依序以表1~3所示比例添加(C)胺系硬化促進劑、(D)多官能硫醇化合物及(E)硬化劑，進行攪拌，得到自由基聚合性樹脂組成物。對於如此方式所得之自由基聚合性樹脂組成物，藉由下述方法測定硬化性並評估。其結果示於表1~3。To the mixture of the above-mentioned (A) component and (B) component, (B) radically polymerizable unsaturated monomer was added, and the mass ratio of (A) component/(B) component was 65/35 to obtain the composition of ( A preparatory sample consisting of A) component and (B) component. Next, to 100 parts by mass of the preliminary sample, that is, 100 parts by mass of the total of (A) component and (B) component, (C) amine-based curing accelerator and (D) were sequentially added in the proportions shown in Tables 1 to 3. ) of the polyfunctional thiol compound and (E) the curing agent, and stirred to obtain a radically polymerizable resin composition. About the radically polymerizable resin composition obtained in this way, hardenability was measured and evaluated by the following method. The results are shown in Tables 1 to 3.

比較例1 　　除了不含有(D)多官能硫醇化合物以外，係與實施例1同樣地得到自由基聚合性樹脂組成物。自由基聚合性樹脂組成物之各成分含量示於表1。對於如此方式所得到之自由基聚合性樹脂組成物，同樣地測定硬化性並評估。其結果示於表1。Comparative Example 1 A radically polymerizable resin composition was obtained in the same manner as in Example 1, except that the (D) polyfunctional thiol compound was not contained. Table 1 shows the content of each component of the radically polymerizable resin composition. Curability was similarly measured and evaluated about the radically polymerizable resin composition obtained in this way. The results are shown in Table 1.

＜於25℃環境下之硬化性測定＞ 　　藉由以下所示之評估法，進行凝膠化時間、硬化溫度、硬化時間之評估。 　　將樹脂組成物調整為25℃，置入試驗管(外徑18mm、長度165mm)中至深度100mm，設置於設定為25℃之恆溫槽中，藉由熱電偶測定樹脂組成物之溫度。測定樹脂組成物之溫度由25℃至成為35℃為止所花的時間，作為凝膠化時間(單位：分鐘)。 　　又，將樹脂組成物到達最高發熱溫度為止的時間定義為最小硬化時間、此時的發熱溫度定義為硬化溫度，根據JIS K-6901-2008 來測定。 ＜於10℃環境下之硬化性測定＞ 　　除了將樹脂組成物之溫度及測定環境溫度設為10℃以外，係與上述25℃硬化性同樣地進行評估。<The measurement of hardening in 25 degreeC environment> By the evaluation method shown below, the evaluation of the gelation time, hardening temperature, and hardening time was performed. The resin composition was adjusted to 25°C, placed in a test tube (outer diameter 18mm, length 165mm) to a depth of 100mm, set in a constant temperature bath set at 25°C, and the temperature of the resin composition was measured by a thermocouple. The time taken until the temperature of the resin composition was changed from 25°C to 35°C was measured as the gelation time (unit: minute). In addition, the time until the resin composition reaches the maximum exothermic temperature is defined as the minimum curing time, and the exothermic temperature at this time is defined as the curing temperature, and it is measured according to JIS K- 6901-2008 . <The measurement of hardenability in 10 degreeC environment> Except having made the temperature of the resin composition and the measurement environment temperature into 10 degreeC, it evaluated similarly to the said 25 degreeC hardenability.

Figure 02_image011
Figure 02_image011

Figure 02_image013
Figure 02_image013

Figure 02_image015
Figure 02_image015

如表1~3所示，含有多官能硫醇化合物之本發明之自由基聚合性樹脂組成物，可知於25℃及低溫之10℃環境下亦如凝膠化時間及最小硬化時間所示，可得到快速硬化性。 　　特別是可知多官能硫醇化合物之總量為0.5質量份以上之實施例，硬化速度更快。又，0.3質量份以上之實施例中，藉由展現鏈轉移劑效果，顯示由凝膠化時間至最小硬化時間為止的時間會延長的傾向，可知藉由得到溫和的硬化過程，可緩和劇烈的硬化收縮。 　　相對於此，不含有多官能硫醇化合物之比較例1之自由基聚合性樹脂組成物，可知相較於實施例1~22之樹脂組成物而言，硬化性緩慢，由凝膠化時間至最小硬化時間為止的時間短。As shown in Tables 1 to 3, the radically polymerizable resin composition of the present invention containing the polyfunctional thiol compound can be found to have gelation time and minimum hardening time at 25°C and a low temperature of 10°C. Rapid hardening can be obtained. In particular, it was found that the hardening speed was faster in the examples in which the total amount of the polyfunctional thiol compound was 0.5 parts by mass or more. In addition, in Examples of 0.3 parts by mass or more, since the chain transfer agent effect was exhibited, the time from the gelation time to the minimum hardening time tended to be prolonged, and it was found that by obtaining a mild hardening process, the severe hardening could be alleviated. hardening shrinkage. On the other hand, the radically polymerizable resin composition of Comparative Example 1, which does not contain a polyfunctional thiol compound, has slow curability compared with the resin compositions of Examples 1 to 22, ranging from gelation time to The time until the minimum hardening time is short.

實施例18~34 　　使用實施例1所用的(A)成分/(B)成分之質量比為65/35之混合物與前述之(C)胺系硬化促進劑、(D)多官能硫醇化合物、(E)硬化劑及以下記載的(F)填充材料。 　　(F)填充材料 　　(1)二氧化矽砂、(有)竹折礦業所製、製品名：矽砂8號 　　(2)碳酸鈣、日東粉化工業(股)、製品名：S light#1200、平均粒子徑：2.6μmExamples 18 to 34 The mixture of (A) component/(B) component used in Example 1 having a mass ratio of 65/35, the aforementioned (C) amine-based hardening accelerator, (D) polyfunctional thiol compound, (E) Hardener and (F) Filler described below. (F) Filling materials (1) Silica sand, (yes) manufactured by Zhuzhe Mining, product name: No. 8 silica sand (2) Calcium carbonate, Nitto Powder Chemical Industry Co., Ltd., product name: S light #1200 , Average particle size: 2.6μm

與實施例1同樣地，以表4~6所示比例對(A)成分及(B)成分之合計100質量份，依序添加(C)胺系硬化促進劑、(D)多官能硫醇化合物及(E)硬化劑並攪拌，得到不含有(F)填充材料之自由基聚合性樹脂組成物。進一步以表4~6所示比例添加(F)填充材料並攪拌，得到構造物修復材料。 　　構造物修復材料之各成分含量示於表4~6。 　　之後，使用所得之構造物修復材料，藉由以下所示方法製作接著試驗用之試驗體。 　　對於如此方式所得之構造物修復材料，藉由下述方法測定接著性，作為接著性評估。其結果示於表4~6。In the same manner as in Example 1, (C) an amine-based curing accelerator and (D) a polyfunctional thiol were sequentially added to 100 parts by mass of the total of (A) components and (B) components at the ratios shown in Tables 4 to 6. The compound and the (E) hardener are stirred to obtain a radically polymerizable resin composition that does not contain the (F) filler. Further, the filler (F) was added and stirred in the proportions shown in Tables 4 to 6 to obtain a structure repair material. The content of each component of the structural repair material is shown in Tables 4-6. Then, using the obtained structural repair material, a test body for the subsequent test was produced by the method shown below. For the structural repair material obtained in this way, the adhesiveness was measured by the following method as an adhesiveness evaluation. The results are shown in Tables 4 to 6.

＜接著試驗用試驗體之製作方法＞ 　　於後述彎曲荷重試驗用試驗體之製作方法中所用的長度×寬度×厚度=70mm×70mm×20mm之JIS K 5600水泥砂漿板1枚之上，將上述所得之構造物修復材料於環境溫度25℃、濕度50%環境下以3mm之厚度成型，將上部於經薄膜密閉之狀態下硬化。之後，於相同環境下硬化24小時。接著，將表面之薄膜剝離，將表面以#240砂紙粗化，對表面送風，藉由丙酮脫脂而洗淨。之後，將接著試驗用之直徑20mm之端子(dolly)以環氧接著劑固著，為了於環境溫度25℃、濕度50%環境下展現接著劑之強度，係固著硬化5小時作為接著試驗用試驗體。<Manufacturing method of test body for subsequent test> On one JIS K 5600 cement mortar board of length×width×thickness=70mm×70mm×20mm used in the manufacture method of test body for bending load test described later, the above obtained The structural repair material is molded with a thickness of 3mm in an ambient temperature of 25°C and a humidity of 50%, and the upper part is hardened in a state sealed by a film. After that, it was hardened in the same environment for 24 hours. Next, the film on the surface was peeled off, the surface was roughened with #240 sandpaper, air was blown to the surface, and the surface was degreased and washed with acetone. After that, the terminal (dolly) with a diameter of 20 mm for the adhesion test was fixed with epoxy adhesive, and in order to show the strength of the adhesive in the environment of ambient temperature of 25°C and humidity of 50%, it was fixed and hardened for 5 hours as the adhesion test. test body.

＜接著試驗＞ 　　對於上述所得之接著試驗用試驗體，於溫度23℃、濕度50%之試驗環境下，使用Elcometer製黏著力試驗器、測定範圍0~7.0MPa、手動式，來測定接著力。接著力之測定，係針對接著試驗用試驗體各進行2次。然後將2次測定結果之平均值，使用於評估接著力。<Adhesion test> For the test body for the adhesion test obtained above, in a test environment with a temperature of 23°C and a humidity of 50%, the adhesive force was measured using an Elcometer adhesive force tester, a measuring range of 0 to 7.0 MPa, and a manual type. The measurement of the adhesion force was carried out twice for each of the test specimens for the adhesion test. Then, the average value of the two measurement results was used to evaluate the adhesion.

比較例2 　　除了不含有(D)多官能硫醇化合物以外，係與實施例18同樣地得到構造物修復材料。之後，與實施例18同樣地製作接著試驗用試驗體，進行接著試驗。又，比較例2之硬化性，係與上述同樣地，係以與實施例18近似的方式，藉由聚合抑制劑來調整，藉由設為凝膠化時間7.0min消除硬化性之不同所致的影響。其結果示於表4。Comparative Example 2 A structure repair material was obtained in the same manner as in Example 18, except that the (D) polyfunctional thiol compound was not contained. After that, in the same manner as in Example 18, a test body for an adhesion test was produced, and an adhesion test was performed. In addition, the curability of Comparative Example 2 was adjusted by a polymerization inhibitor in a similar manner to Example 18 as described above, and the difference in curability was eliminated by setting the gelation time to 7.0 min. Impact. The results are shown in Table 4.

Figure 02_image017
Figure 02_image017

Figure 02_image019
Figure 02_image019

Figure 02_image021
Figure 02_image021

如表4~6所示，可知實施例18~34之含有多官能硫醇化合物的本發明之接著試驗用試驗體，可得到強的接著性。 　　相對於此，比較例2，相較於實施例18~34之接著試驗用試驗體而言，接著性低。As shown in Tables 4 to 6, it was found that the test specimens for the adhesive test of the present invention containing the polyfunctional thiol compound of Examples 18 to 34 had strong adhesive properties. On the other hand, in Comparative Example 2, the adhesion was lower than that of the test specimens for the adhesion test of Examples 18 to 34.

實施例35~41 　　使用實施例1中所用的(A)成分/(B)成分之質量比為65/35之混合物與前述(C)胺系硬化促進劑、(D)多官能硫醇化合物、(E)硬化劑及以下記載的(F)填充材料。 　　(F)填充材料 　　(1)二氧化矽砂、(有)竹折礦業所製、製品名：矽砂8號 　　(2)碳酸鈣、日東粉化工業(股)、製品名：S light#1200、平均粒子徑：2.6μmExamples 35 to 41 The mixture of (A) component/(B) component used in Example 1 having a mass ratio of 65/35 and the aforementioned (C) amine-based hardening accelerator, (D) polyfunctional thiol compound, (E) Hardener and (F) Filler described below. (F) Filling materials (1) Silica sand, (yes) manufactured by Zhuzhe Mining, product name: No. 8 silica sand (2) Calcium carbonate, Nitto Powder Chemical Industry Co., Ltd., product name: S light #1200 , Average particle size: 2.6μm

與實施例1同樣地，以表7所示比例，對(A)成分及(B)成分之混合物100質量份，依序以表7所示比例添加(C)胺系硬化促進劑、(D)多官能硫醇化合物及(E)硬化劑並攪拌，得到不含有(F)填充材料之自由基聚合性樹脂組成物。進一步以表7所示比例添加(F)填充材料並攪拌，得到構造物修復材料。 　　構造物修復材料之各成分含量示於表7。 　　之後，使用所得之構造物修復材料，藉由以下所示方法製作彎曲荷重試驗用之試驗體。 　　對於使用如此方式所得之構造物修復材料所得到的彎曲荷重試驗用之試驗體，藉由下述方法測定彎曲荷重，作為所修復之構造物的彎曲強度之評估。其結果示於表7。In the same manner as in Example 1, at the ratio shown in Table 7, to 100 parts by mass of the mixture of (A) component and (B) component, (C) an amine-based hardening accelerator and (D) were sequentially added at the ratio shown in Table 7. ) The polyfunctional thiol compound and the (E) curing agent were stirred to obtain a radically polymerizable resin composition that did not contain the (F) filler. Further, the filler (F) was added in the proportion shown in Table 7 and stirred to obtain a structure repair material. The content of each component of the structural repair material is shown in Table 7. Then, using the obtained structural repair material, a test body for bending load test was produced by the method shown below. With respect to the test body for bending load test obtained by using the structure repair material obtained in this way, the bending load is measured by the following method as an evaluation of the bending strength of the repaired structure. The results are shown in Table 7.

＜彎曲荷重試驗用試驗體之製作方法＞ 　　如圖1所示，將長度×寬度×厚度=70mm×70mm×20mm之JIS K 5600水泥砂漿板2枚(A、B)，隔著20mm寬度之空間並排於平面，以#240砂紙將側面(與構造物修復材料接觸之面)粗化，將表面以送風洗淨。對所得之長度×寬度×厚度=70mm×20mm×20mm之空間部，於環境溫度25℃、濕度50%環境下注入上述所得之構造物修復材料，將上部以經薄膜密閉的狀態下硬化。之後，於相同環境下硬化24小時，得到圖2所示之彎曲荷重試驗用試驗體。<Manufacturing method of test body for bending load test> As shown in Figure 1, two JIS K 5600 cement mortar boards (A, B) with length x width x thickness = 70mm x 70mm x 20mm are separated by a space of 20mm width Put them side by side on a flat surface, roughen the side surface (the surface in contact with the structure repair material) with #240 sandpaper, and wash the surface with blowing air. The above-obtained structural repair material was injected into the space of the obtained length×width×thickness=70mm×20mm×20mm at an ambient temperature of 25°C and a humidity of 50%, and the upper part was cured in a state sealed by a film. Then, it hardened in the same environment for 24 hours, and the test piece for bending load test shown in FIG. 2 was obtained.

＜彎曲荷重試驗＞ 　　對於上述所得之彎曲荷重試驗用試驗體，於溫度23℃、濕度50%之試驗環境下，使用(股)Orientec製Tensilon UTC-1T，以支點間距離40mm、試驗速度1mm/min，對彎曲荷重試驗用試驗體之構造物修復材料硬化部分的中心部表面線狀部分(長度70mm)施加荷重，測定彎曲荷重。施加荷重直到荷重試驗用試驗體斷裂為止，測定至斷裂為止的最大荷重。彎曲荷重之測定，係對於彎曲荷重試驗用試驗體各進行2次。然後將2次測定結果之平均值使用於彎曲荷重之評估。彎曲荷重試驗(N)之值越高，表示所修復之構造物的彎曲強度越優良。<Bending load test> For the test body for bending load test obtained above, use Tensilon UTC-1T manufactured by Orientec in a test environment with a temperature of 23°C and a humidity of 50%, the distance between the fulcrums is 40mm, and the test speed is 1mm/ min, a load was applied to the linear portion (length 70 mm) of the central surface of the hardened portion of the structural repair material of the test body for the bending load test, and the bending load was measured. A load was applied until the specimen for a load test broke, and the maximum load until the break was measured. The measurement of the bending load was carried out twice for each of the specimens for the bending load test. The average value of the 2 measurement results was then used for the evaluation of the bending load. The higher the value of the bending load test (N), the better the bending strength of the repaired structure.

比較例3 　　除了不含有(D)多官能硫醇化合物以外，係與實施例35同樣地得到構造物修復用樹脂組成物。又，比較例3之硬化性，係以與實施例37近似的方式，藉由聚合抑制劑來調整，藉由設為凝膠化時間7.0min消除硬化性之不同所致的影響。Comparative Example 3 A resin composition for repairing a structure was obtained in the same manner as in Example 35, except that the (D) polyfunctional thiol compound was not contained. In addition, the curability of Comparative Example 3 was adjusted by a polymerization inhibitor in a manner similar to that of Example 37, and the influence of the difference in curability was eliminated by setting the gelation time to 7.0 min.

Figure 02_image023
Figure 02_image023

如表7所示，可知實施例35~41之含有多官能硫醇化合物的本發明之彎曲荷重試驗用試驗體，補修材與砂漿板之層間的接著性優良，因此可得到高的彎曲強度。相對於此，比較例3，相較於實施例35~41之彎曲荷重試驗用試驗體而言，彎曲強度低。此係因實施例35~41之彎曲荷重試驗用試驗體，相較於比較例3之彎曲荷重試驗用試驗體而言，構造物修復材料與水泥砂漿板之接著性良好所致。As shown in Table 7, the test specimens for bending load test of the present invention containing the polyfunctional thiol compound of Examples 35 to 41 were found to have excellent adhesion between the layers of the repair material and the mortar board, so that high bending strength was obtained. On the other hand, in Comparative Example 3, the bending strength was lower than that of the specimens for bending load tests of Examples 35 to 41. This is because the test body for bending load test of Examples 35 to 41 has good adhesion between the structural repair material and the cement mortar board compared to the test body for bending load test of Comparative Example 3.

再者，前述表1~7中，表中之組成物編號相同的情況時，表示係使用相同的自由基聚合性樹脂組成物[(A)成分~(E)成分]。 [產業上之可利用性]In addition, in the said Tables 1-7, when the composition number in a table|surface is the same, it shows that the same radical polymerizable resin composition [(A) component - (E) component] was used. [Industrial Availability]

本發明之自由基聚合性樹脂組成物及構造物修復材料，具有低溫硬化性，且具有優良之接著強度。即使於低溫環境下亦可快速硬化，且具有優良的接著強度，因此不易產生固著/乾燥後之斷裂或修復部位與修復材料界面之剝離。因此，藉由使用本發明之構造物修復材料，對經常伴隨振動之混凝土構造物，可良好地進行龜裂部分之修復。亦即，固著時可展現優良的附著強度，可適合地使用於混凝土構造物等之龜裂的修復。The radically polymerizable resin composition and structural repair material of the present invention have low-temperature curability and excellent adhesive strength. It can harden quickly even in low temperature environment, and has excellent bonding strength, so it is not easy to cause fracture after fixing/drying or peeling of the interface between the repaired part and the repairing material. Therefore, by using the structure repairing material of the present invention, the repair of the cracked part can be performed favorably for the concrete structure which is often accompanied by vibration. That is, excellent adhesion strength can be exhibited at the time of fixing, and it can be suitably used for repairing cracks in concrete structures and the like.

[圖1]顯示為了使用本發明之構造物修復材料來製成彎曲荷重試驗用試驗體所用的水泥砂漿(cement mortar)板2枚的平面圖與橫方向截面圖之示意圖。 　　[圖2]顯示使用本發明之構造物修復材料所得到之彎曲荷重試驗用試驗體的平面圖與橫方向截面圖之示意圖。Fig. 1 is a schematic diagram showing a plan view and a transverse cross-sectional view of two cement mortar boards used to prepare a test body for a bending load test using the structural repair material of the present invention. Fig. 2 is a schematic diagram showing a plan view and a transverse cross-sectional view of a test body for a bending load test obtained by using the structural repair material of the present invention.

Claims (13)

一種自由基聚合性樹脂組成物，其特徵為含有(A)自由基聚合性樹脂、(B)自由基聚合性不飽和單體、(C)胺系硬化促進劑，與(D)多官能硫醇化合物，前述自由基聚合性樹脂組成物，不含有由金屬皂及具有β-二酮骨架之金屬錯合物中選出的1種以上之含金屬化合物，前述(A)成分為胺基甲酸酯(甲基)丙烯酸酯樹脂，前述(C)成分為選自由N,N-雙(2-羥基乙基)-p-甲苯胺、N,N-雙(2-羥基丙基)-p-甲苯胺、N,N-雙(2-羥基乙基)苯胺所成之群的至少1種，以前述(A)成分與前述(B)成分之合計量為100質量份時，前述(D)成分之含量為0.1~20質量份。 A radically polymerizable resin composition characterized by containing (A) a radically polymerizable resin, (B) a radically polymerizable unsaturated monomer, (C) an amine-based hardening accelerator, and (D) a polyfunctional sulfur The alcohol compound, the radically polymerizable resin composition described above, does not contain one or more metal-containing compounds selected from metal soaps and metal complexes having a β-diketone skeleton, wherein the component (A) is urethane Ester (meth)acrylate resin, the component (C) is selected from N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxypropyl)-p- At least one of the group consisting of toluidine and N,N-bis(2-hydroxyethyl)aniline, when the total amount of the above-mentioned (A) component and the above-mentioned (B) component is 100 parts by mass, the above-mentioned (D) The content of the ingredients is 0.1 to 20 parts by mass. 如請求項1之自由基聚合性樹脂組成物，其中前述(D)成分，為具有下述通式(Q)表示之構造的化合物；
Figure 107121788-A0305-02-0056-1
 (通式(Q)中，R1及R2，係分別獨立地為氫原子、碳數 1~10之烷基或碳數6~18之芳香族基；*表示係連結於具有至少1個巰基之任意有機基；a為0~2之整數)。 The radically polymerizable resin composition according to claim 1, wherein the component (D) is a compound having a structure represented by the following general formula (Q);
Figure 107121788-A0305-02-0056-1
 (In the general formula (Q), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms; Any organic group of mercapto group; a is an integer of 0~2). 如請求項1或2之自由基聚合性樹脂組成物，其中前述(D)成分，為具有下述通式(Q-1)表示之構造的化合物；
Figure 107121788-A0305-02-0057-2
 (通式(Q-1)中，R1及R2，係分別獨立地為氫原子、碳數1~10之烷基或碳數6~18之芳香族基；**表示係連結於具有至少1個巰基之任意有機基；a為0~2之整數)。 The radically polymerizable resin composition according to claim 1 or 2, wherein the component (D) is a compound having a structure represented by the following general formula (Q-1);
Figure 107121788-A0305-02-0057-2
 (In the general formula (Q-1), R 1 and R 2 are independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms; Any organic group with at least one mercapto group; a is an integer from 0 to 2). 如請求項1或2之自由基聚合性樹脂組成物，其中前述(D)成分，為選自2~6官能之多官能硫醇化合物的至少1種。 The radically polymerizable resin composition according to claim 1 or 2, wherein the component (D) is at least one selected from the group consisting of 2-6 functional polyfunctional thiol compounds. 如請求項1或2之自由基聚合性樹脂組成物，其中以前述(A)成分與前述(B)成分之合計量為100質量份時，前述(A)成分之含量為5~95質量份、前述(B)成分之含量為5~95質量份、前述成分(C)之含量為0.01~10質量份。 The radically polymerizable resin composition according to claim 1 or 2, wherein the content of the component (A) is 5 to 95 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass. . The content of the aforementioned component (B) is 5 to 95 parts by mass, and the content of the aforementioned component (C) is 0.01 to 10 parts by mass. 如請求項1或2之自由基聚合性樹脂組成物，其進一步含有(E)硬化劑。 The radically polymerizable resin composition according to claim 1 or 2, which further contains (E) a hardener. 如請求項6之自由基聚合性樹脂組成物，其中以前述(A)成分與前述(B)成分之合計量為100質量份時，前述(E)成分之含量為0.1~10質量份。 The radical polymerizable resin composition according to claim 6, wherein the content of the component (E) is 0.1 to 10 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass. 如請求項6之自由基聚合性樹脂組成物，其中前述(E)成分，含有選自由二苯甲醯基過氧化物、苯甲醯基m-甲基苯甲醯基過氧化物、m-甲苯甲醯基過氧化物、甲基乙基酮過氧化物、異丙苯氫過氧化物、過氧苯甲酸t-丁酯所成之群的至少1種。 The radically polymerizable resin composition according to claim 6, wherein the component (E) contains a compound selected from the group consisting of dibenzyl peroxide, benzyl m-methylbenzyl peroxide, m- At least one of the group consisting of toluyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, and t-butyl peroxybenzoate. 一種構造物修復材料，其含有如請求項1~8中任一項之自由基聚合性樹脂組成物。 A structure repair material, which contains the radically polymerizable resin composition according to any one of claims 1 to 8. 一種構造物修復材料，其含有如請求項1~8中任一項之自由基聚合性樹脂組成物及(F)填充材料。 A structure repair material comprising the radically polymerizable resin composition according to any one of claims 1 to 8 and (F) a filler. 如請求項10之構造物修復材料，其中以前述(A)成分與前述(B)成分之合計量為100質量份時，前述(F)成分之含量為1~700質量份。 The structural repair material according to claim 10, wherein when the total amount of the component (A) and the component (B) is 100 parts by mass, the content of the component (F) is 1 to 700 parts by mass. 如請求項10或11之構造物修復材料，其中前述(F)成分，為選自由矽砂、碳酸鈣、滑石及發煙二氧化矽所成之群的至少1種。 The structural repair material according to claim 10 or 11, wherein the component (F) is at least one selected from the group consisting of silica sand, calcium carbonate, talc, and fumed silica. 如請求項9~11中任一項之構造物修復材料，其中前述構造物修復材料，為版式軌道之構造物修復材料。 The structural repair material according to any one of Claims 9 to 11, wherein the aforementioned structural repair material is a structural repair material for a layout track.
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