TW202006076A - Self-healing coating agent, cured product and film including hydroxyl-containing (meth) acrylic resin, hydroxyl-containing polysiloxane, polyisocyanates and polycarbonate polyols - Google Patents

Self-healing coating agent, cured product and film including hydroxyl-containing (meth) acrylic resin, hydroxyl-containing polysiloxane, polyisocyanates and polycarbonate polyols Download PDF

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TW202006076A
TW202006076A TW108124543A TW108124543A TW202006076A TW 202006076 A TW202006076 A TW 202006076A TW 108124543 A TW108124543 A TW 108124543A TW 108124543 A TW108124543 A TW 108124543A TW 202006076 A TW202006076 A TW 202006076A
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polyisocyanate
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橋本祐希
久米啓太
山崎彰寬
東本徹
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日商荒川化學工業股份有限公司
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    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C09D179/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • C09D183/06Polysiloxanes containing silicon bound to oxygen-containing groups

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Abstract

The present invention provides a self-healing coating agent, a cured product, and a film. The present invention provides a self-healing coating agent, a cured product thereof, and a film containing the cured product, wherein the self-healing coating agent includes a hydroxyl-containing (meth) acrylic resin, a hydroxyl-containing polysiloxane, a polyisocyanates and a polycarbonate polyols. In one embodiment, the polyisocyanates of the self-healing coating agent include two or more selected from an adduct of the polyisocyanates, an allophanate body of the polyisocyanates, a biuret body of the polyisocyanates, and an isocyanurate body of the polyisocyanates.

Description

自我修復性塗覆劑、硬化物及薄膜 Self-healing coating agent, hardened material and film

本發明係關於一種自我修復性塗覆劑、硬化物及薄膜。 The invention relates to a self-healing coating agent, hardened material and film.

在電子設備、汽車用部件等各種工業製品中,使用ABS、聚碳酸酯等塑膠基材。為了保護如此之塑膠基材,利用塗覆劑進行表面處理。此等塗覆劑中,自我修復性塗覆劑由於所產生的損傷會隨時間消失,因此,在保護各種基材方面是理想的塗覆劑。 Plastic substrates such as ABS and polycarbonate are used in various industrial products such as electronic equipment and automotive parts. In order to protect such plastic substrates, surface treatment is performed with coating agents. Among these coating agents, the self-healing coating agent will disappear with time due to the damage generated, so it is an ideal coating agent in protecting various substrates.

作為與此等塗覆劑相關的先前技術,例如已知揭露了含有胺基甲酸酯(甲基)丙烯酸酯類樹脂(a)、氟類化合物(b)及光聚合引發劑(d)的塗覆劑的專利文獻1。 As a prior art related to these coating agents, for example, it is known to disclose a urethane (meth)acrylate-based resin (a), a fluorine-based compound (b), and a photopolymerization initiator (d) Patent Document 1 for coating agent.

【先前技術文獻】【Prior Technical Literature】 【專利文獻】【Patent Literature】

【專利文獻1】日本專利第6241571號公報 [Patent Document 1] Japanese Patent No. 6241571

在專利文獻1中,雖然記載自我修復性、耐污染性優良,但是,對於加工性可以進行進一步改良。 Patent Document 1 describes that it is excellent in self-healing property and contamination resistance, but it can be further improved in workability.

本發明所欲解決之技術問題在於:提供一種用於製造加工性優良的硬化物、薄膜的自我修復性塗覆劑;提供一種用於製造透明性優良且塗布外觀良好的硬化物、薄膜的自我修復性塗覆劑;提供一種用於製造具有防污性的硬化物、薄膜的自我修復性塗覆劑。 The technical problem to be solved by the present invention is to provide a self-healing coating agent for manufacturing hardened materials and films with excellent processability; and to provide a self-repairing coating material for manufacturing hardened materials and films with excellent transparency and good appearance. Repairing coating agent; providing a self-repairing coating agent for manufacturing anti-fouling hardened materials and films.

本發明人進行深入研究,結果發現,利用含有特定成分的自我修復性塗覆劑可解決上述技術問題。 The inventors conducted intensive studies and found that the above-mentioned technical problems can be solved by using self-healing coating agents containing specific ingredients.

藉由本發明,提供以下項目。 With the present invention, the following items are provided.

(項目1) (Item 1)

一種自我修復性塗覆劑,其特徵係含有含羥基的(甲基)丙烯酸樹脂、含羥基的聚矽氧烷(silicone)、多異氰酸酯及聚碳酸酯多元醇。 A self-healing coating agent characterized by containing hydroxyl-containing (meth)acrylic resin, hydroxyl-containing silicone, polyisocyanate and polycarbonate polyol.

(項目2) (Item 2)

如上述項目所記載之自我修復性塗覆劑,其中,前述多異氰酸酯包含選自多異氰酸酯的加成物、多異氰酸酯的脲基甲酸酯體、多異氰酸酯的縮二脲體及多異氰酸酯的異氰脲酸酯體中的兩種以上。 The self-healing coating agent as described in the above item, wherein the polyisocyanate contains an isocyanate selected from polyisocyanate, allophanate of polyisocyanate, biuret of polyisocyanate and isocyanate of polyisocyanate Two or more of cyanurate.

(項目3) (Item 3)

如上述項目1或2所記載之自我修復性塗覆劑,其中,前述含羥基的(甲基)丙烯酸樹脂的玻璃轉變溫度為40~100℃。 The self-healing coating agent as described in the above item 1 or 2, wherein the glass transition temperature of the hydroxyl group-containing (meth)acrylic resin is 40 to 100°C.

(項目4) (Item 4)

如上述項目1~3中任一項所記載之自我修復性塗覆劑,其中,前述聚碳酸酯多元醇的數均分子量為800~1000。 The self-healing coating agent as described in any one of items 1 to 3 above, wherein the polycarbonate polyol has a number average molecular weight of 800 to 1,000.

(項目5) (Item 5)

如上述項目1~4中任一項所記載之自我修復性塗覆劑,其中,將前述含羥基的(甲基)丙烯酸樹脂、含羥基的聚矽氧烷、多異氰酸酯及聚碳酸酯多元醇的總含量設為100質量%時,含羥基的(甲基)丙烯酸樹脂的含量為30~70質量%,含羥基的聚矽氧烷的含量為1~10質量%,多異氰酸酯的含量為10~50質量%,聚碳酸酯多元醇的含量為15~40質量%。 The self-healing coating agent according to any one of items 1 to 4 above, wherein the aforementioned hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, polyisocyanate and polycarbonate polyol When the total content is set to 100% by mass, the content of hydroxyl-containing (meth)acrylic resin is 30 to 70% by mass, the content of hydroxyl-containing polysiloxane is 1 to 10% by mass, and the content of polyisocyanate is 10 ~50% by mass, and the content of polycarbonate polyol is 15~40% by mass.

(項目6) (Item 6)

一種硬化物,其特徵係其為如上述項目1~5中任一項所記載之自我修復性塗覆劑的硬化物。 A hardened product characterized in that it is a hardened product of the self-healing coating agent described in any one of items 1 to 5 above.

(項目7) (Item 7)

一種薄膜,其特徵係含有上述項目6所記載之硬化物。 A film characterized by containing the hardened product described in item 6 above.

在本發明中,關於上述的一個或多個特徵,除了明確記載的組合以外,可進一步組合來提供。 In the present invention, the one or more features described above can be provided in combination in addition to the combinations explicitly described.

藉由使用本發明的自我修復性塗覆劑,可以得到加工性優良且伸長率良好的硬化物及薄膜、透明性優良且塗布外觀良好的硬化物及薄膜、防污性良好的硬化物及薄膜。 By using the self-healing coating agent of the present invention, a cured product and a film with excellent processability and good elongation, a cured product and a film with excellent transparency and a good coating appearance, and a cured product and a film with good antifouling properties can be obtained .

在本發明整體中,各物性值、含量等的數值範圍可適當(例如從下述各項目所記載的上限及下限的值選擇)設定。具體而言,對於數值α,在數值α的上限可例示A1、A2、A3等、且數值α的下限可例示B1、B2、B3等的情況下,數值α的範圍可例示出A1以下、A2以下、A3以下、B1以上、B2以上、B3以上、A1~B1、A1~B2、A1~B3、A2~B1、A2~B2、A2~B3、A3~B1、A3~B2、A3~B3等。 In the whole of the present invention, the numerical range of each physical property value, content, etc. can be appropriately set (for example, selected from the values of the upper limit and the lower limit described in the following items). Specifically, for the value α, when the upper limit of the value α can be exemplified by A1, A2, A3, etc., and the lower limit of the value α can be exemplified by B1, B2, B3, etc., the range of the value α can be exemplified by A1 or less, A2 Below, below A3, above B1, above B2, above B3, above A1~B1, A1~B2, A1~B3, A2~B1, A2~B2, A2~B3, A3~B1, A3~B2, A3~B3, etc. .

[自我修復性塗覆劑] [Self-repairing coating agent]

本發明提供一種含有含羥基的(甲基)丙烯酸樹脂、含羥基的聚矽氧烷、多異氰酸酯及聚碳酸酯多元醇的自我修復性塗覆劑。 The invention provides a self-healing coating agent containing hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, polyisocyanate and polycarbonate polyol.

<含羥基的(甲基)丙烯酸樹脂> <Hydroxy-containing (meth)acrylic resin>

含羥基的(甲基)丙烯酸樹脂,可例示含有源自不含羥基的(甲基)丙烯酸烷酯的構成單元及源自含羥基的(甲基)丙烯酸烷酯的構成單元的共聚物等。 含羥基的(甲基)丙烯酸樹脂可以單獨使用,亦可以組合使用兩種以上。 The hydroxyl group-containing (meth)acrylic resin may, for example, be a copolymer containing a constitutional unit derived from a hydroxyl-free alkyl (meth)acrylate and a hydroxyl group-containing alkyl (meth)acrylate. The hydroxyl group-containing (meth)acrylic resin may be used alone or in combination of two or more.

在本發明中,「(甲基)丙烯酸」是指「選自由丙烯酸及甲基丙烯酸所成群中的至少一種」。同樣地,「(甲基)丙烯酸酯」是指「選自由丙烯酸酯及甲基丙烯酸酯所成群中的至少一種」。此外,「(甲基)丙烯醯基」是指「選自由丙烯醯基及甲基丙烯醯基所成群中的至少一種」。 In the present invention, "(meth)acrylic acid" means "at least one selected from the group consisting of acrylic acid and methacrylic acid". Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". In addition, "(meth)acryloyl" means "at least one selected from the group consisting of acryloyl and methacryloyl".

(不含羥基的(甲基)丙烯酸烷酯) (Hydroxy-free alkyl (meth)acrylate)

不含羥基的(甲基)丙烯酸烷酯由下述通式表示。 The alkyl (meth)acrylate not containing a hydroxyl group is represented by the following general formula.

【化1】

Figure 108124543-A0202-12-0005-1
【Chemistry 1】
Figure 108124543-A0202-12-0005-1

(式中,Ra1為氫原子或甲基,Ra2為烷基。) (In the formula, R a1 is a hydrogen atom or a methyl group, and R a2 is an alkyl group.)

不含羥基的(甲基)丙烯酸烷酯可以單獨使用或使用兩種以上。 The alkyl (meth) acrylate which does not contain a hydroxyl group can be used individually or in combination of 2 or more types.

烷基,可例示直鏈烷基、支鏈烷基、環烷基等。 The alkyl group can be exemplified by straight chain alkyl groups, branched chain alkyl groups, cycloalkyl groups, and the like.

直鏈烷基由通式-CnH2n+1(n為1以上的整數)表示。直鏈烷基,可例示甲基、乙基、丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正十甲基等。 The linear alkyl group is represented by the general formula -C n H 2n+1 (n is an integer of 1 or more). Examples of straight-chain alkyl groups include methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decylmethyl groups.

支鏈烷基為直鏈烷基中的至少一個氫被烷基取代後的基團。支鏈烷基,可例示二乙基戊基、三甲基丁基、三甲基戊基、三甲基己基等。 A branched alkyl group is a group in which at least one hydrogen in a linear alkyl group is substituted with an alkyl group. Examples of branched alkyl groups include diethylpentyl, trimethylbutyl, trimethylpentyl, and trimethylhexyl.

環烷基,可例示單環環烷基、橋環環烷基、稠環環烷基等。 Examples of cycloalkyl groups include monocyclic cycloalkyl groups, bridged cycloalkyl groups, and condensed ring cycloalkyl groups.

單環環烷基,可例示環戊基、環己基、環庚基、環癸基、3,5,5-三甲基環己基等。 Examples of monocyclic cycloalkyls include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, 3,5,5-trimethylcyclohexyl and the like.

橋環環烷基,可例示三環癸基、金剛烷基、降莰基等。 Examples of bridged cycloalkyls include tricyclodecyl, adamantyl, and norbornyl.

稠環環烷基,可例示雙環癸基等。 Examples of the fused ring cycloalkyl include bicyclodecyl.

不含羥基的(甲基)丙烯酸烷酯,可例示不含羥基的(甲基)丙烯酸直鏈烷酯、不含羥基的(甲基)丙烯酸支鏈烷酯、不含羥基的(甲基)丙烯酸環烷酯等。 Alkyl (meth)acrylates that do not contain hydroxyl groups can be exemplified by linear alkyl (meth)acrylates that do not contain hydroxyl groups, branched alkyl (meth)acrylates that do not contain hydroxyl groups, and (meth) groups that do not contain hydroxyl groups Naphthenic acrylate, etc.

不含羥基的(甲基)丙烯酸直鏈烷酯,可例示(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基) 丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸十六烷酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸十八烷酯、(甲基)丙烯酸二十烷酯、(甲基)丙烯酸二十二烷酯等。 Straight-chain alkyl (meth)acrylates that do not contain hydroxyl groups can be exemplified by methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, (Meth) hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, cetyl (meth) acrylate, dodecyl (meth) acrylate, deca (meth) acrylate Octane, arachidyl (meth)acrylate, behenyl (meth)acrylate, etc.

不含羥基的(甲基)丙烯酸支鏈烷酯,可例示(甲基)丙烯酸異丙酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸2-乙基己酯等。 Branched alkyl (meth)acrylates without hydroxyl groups, exemplified by isopropyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tri(meth)acrylate Grade butyl ester, 2-ethylhexyl (meth)acrylate, etc.

不含羥基的(甲基)丙烯酸環烷酯,可例示(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯(dicyclopentanyl(meth)acrylate)、(甲基)丙烯酸異莰酯等。 Cycloalkyl (meth)acrylates that do not contain hydroxyl groups can be exemplified by cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (Meth) acrylate, etc.

在一個實施型態中,從有助於自我修復性塗覆劑的流平性、密著性這一點考慮,理想為烷基的碳原子數約1~20的(甲基)丙烯酸烷酯。此外,藉由組合使用烷基的碳原子數不同的不含羥基的(甲基)丙烯酸烷酯,能夠調節含羥基的(甲基)丙烯酸樹脂的玻璃轉變溫度等物性。 In one embodiment, from the viewpoint of contributing to leveling and adhesion of the self-healing coating agent, it is desirable to be an alkyl (meth)acrylate having about 1 to 20 carbon atoms in the alkyl group. In addition, by using a combination of alkyl (meth)acrylates having different alkyl groups with different carbon atoms, it is possible to adjust physical properties such as the glass transition temperature of the hydroxyl-containing (meth)acrylic resin.

在一個實施型態中,不含羥基的(甲基)丙烯酸烷酯中,從特別是有助於自我修復性塗覆劑的耐磨損性、流平性、密著性這一點考慮,理想為(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯。 In one embodiment, among the alkyl (meth)acrylates that do not contain hydroxyl groups, it is desirable from the viewpoint of abrasion resistance, leveling property, and adhesion of the self-healing coating agent in particular. It is methyl (meth)acrylate and butyl (meth)acrylate.

源自不含羥基的(甲基)丙烯酸烷酯的構成單元在含羥基的(甲基)丙烯酸樹脂的全部構成單元100莫耳%中所占的含量的上限可例示98莫耳%、95莫耳%、90莫耳%、85莫耳%、80莫耳%、75莫耳%、70莫耳%、65莫耳%等,下限可例示95莫耳%、90莫耳%、85莫耳%、80莫耳%、75莫耳%、70莫耳%、65莫耳%、62莫耳%等。在一個實施型態中,源自不含羥基的(甲基)丙烯酸烷酯的構成單元在含羥基的(甲基)丙烯酸樹脂的全部構成單 元100莫耳%中所占的含量的範圍理想為約62莫耳%~98莫耳%。 The upper limit of the content of the structural unit derived from the (meth)acrylic acid alkyl ester which does not contain a hydroxyl group in 100 mol% of all the structural units of a (meth)acrylic resin containing a hydroxyl group can be exemplified by 98 mol%, 95 mol Ear%, 90 mole%, 85 mole%, 80 mole%, 75 mole%, 70 mole%, 65 mole%, etc., the lower limit can be exemplified by 95 mole%, 90 mole%, 85 mole %, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 62 mol%, etc. In one embodiment, the content range of the structural unit derived from the (meth)acrylic acid alkyl ester which does not contain a hydroxyl group in 100 mol% of all the structural units of the (meth)acrylic resin containing a hydroxyl group is ideally About 62 mole% to 98 mole%.

源自不含羥基的(甲基)丙烯酸烷酯的構成單元在含羥基的(甲基)丙烯酸樹脂的全部構成單元100質量%中所占的含量的上限可例示98質量%、95質量%、90質量%、85質量%、80質量%、75質量%、70質量%等,下限可例示95質量%、90質量%、85質量%、80質量%、75質量%、70質量%、65質量%等。在一個實施型態中,源自不含羥基的(甲基)丙烯酸烷酯的構成單元在含羥基的(甲基)丙烯酸樹脂的全部構成單元100質量%中所占的含量的範圍理想為約65質量%~98質量%。 The upper limit of the content of the structural unit derived from the (meth)acrylic acid alkyl ester not containing a hydroxyl group in 100% by mass of all the structural units of the (meth)acrylic resin containing a hydroxyl group can be exemplified by 98% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, etc., the lower limit can be exemplified by 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass %Wait. In one embodiment, the range of the content of the structural units derived from the (meth)acrylic acid alkyl ester not containing a hydroxyl group in 100% by mass of all the structural units of the (meth)acrylic resin containing a hydroxyl group is desirably about 65% by mass to 98% by mass.

(含羥基的(甲基)丙烯酸烷酯) (Hydroxy-containing alkyl (meth)acrylate)

含羥基的(甲基)丙烯酸烷酯由下述通式表示。 The hydroxyl group-containing alkyl (meth)acrylate is represented by the following general formula.

Figure 108124543-A0202-12-0007-2
Figure 108124543-A0202-12-0007-2

(式中,Ra3為氫原子或甲基,Ra4為亞烷基。) (In the formula, R a3 is a hydrogen atom or a methyl group, and R a4 is an alkylene group.)

含羥基的(甲基)丙烯酸烷酯可以組合使用兩種以上。 Two or more types of hydroxyl group-containing alkyl (meth)acrylates can be used in combination.

亞烷基,可例示直鏈亞烷基、支鏈亞烷基、亞環烷基等。 The alkylene group may, for example, be a linear alkylene group, a branched alkylene group, or a cycloalkylene group.

含羥基的(甲基)丙烯酸烷酯,可例示含羥基的(甲基)丙烯酸直鏈烷酯、含羥基的(甲基)丙烯酸支鏈烷酯、含羥基的(甲基)丙烯酸環烷酯等。 Hydroxy-containing alkyl (meth)acrylates, exemplified by linear alkyl (meth)acrylates containing hydroxyl, branched alkyl (meth)acrylates containing hydroxyl, cycloalkyl (meth)acrylates containing hydroxyl Wait.

含羥基的(甲基)丙烯酸直鏈烷酯,可例示(甲基)丙烯酸羥甲酯、(甲基)丙烯酸羥乙酯、(甲基)丙烯酸4-羥丁酯等。 Examples of the hydroxyl-containing linear alkyl (meth)acrylate include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

含羥基的(甲基)丙烯酸支鏈烷酯,可例示(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸3-羥丁酯等。 Examples of the hydroxyl-containing branched alkyl (meth)acrylate include 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate.

含羥基的(甲基)丙烯酸環烷酯,可例示(甲基)丙烯酸羥環己酯、(甲基)丙烯酸4-(羥甲基)環己基甲酯等。 Examples of the hydroxyl group-containing cycloalkyl (meth)acrylate include hydroxycyclohexyl (meth)acrylate and 4-(hydroxymethyl)cyclohexyl methyl (meth)acrylate.

關於含羥基的(甲基)丙烯酸烷酯,從自我修復性塗覆劑的硬化性、貯存期等觀點出發,理想為烷基的碳原子數為約1~4的含羥基的(甲基)丙烯酸烷酯。 The hydroxyl group-containing alkyl (meth)acrylate is preferably a hydroxyl group-containing (methyl) group having about 1 to 4 carbon atoms from the viewpoint of the curability of the self-healing coating agent and the shelf life. Alkyl acrylate.

在一個實施型態中,含羥基的(甲基)丙烯酸烷酯中,從自我修復性塗覆劑的硬化性、貯存期等觀點出發,理想為(甲基)丙烯酸2-羥乙酯。 In one embodiment, the hydroxyl group-containing alkyl (meth)acrylate is preferably 2-hydroxyethyl (meth)acrylate from the viewpoint of the hardenability and storage life of the self-healing coating agent.

源自含羥基的(甲基)丙烯酸烷酯的構成單元在含羥基的(甲基)丙烯酸樹脂的全部構成單元100莫耳%中所占的含量的上限可例示38莫耳%、35莫耳%、30莫耳%、25莫耳%、20莫耳%、15莫耳%、10莫耳%、5莫耳%、2.5莫耳%等,下限可例示35莫耳%、30莫耳%、25莫耳%、20莫耳%、15莫耳%、10莫耳%、5莫耳%、2.5莫耳%、1.5莫耳%等。在一個實施型態中,源自含羥基的(甲基)丙烯酸烷酯的構成單元在含羥基的(甲基)丙烯酸樹脂的全部構成單元100莫耳%中所占的含量的範圍理想為約1.5莫耳%~38莫耳%。 The upper limit of the content of the constituent units derived from the hydroxyl group-containing (meth)acrylic acid alkyl ester in 100 mole% of all the constituent units of the hydroxyl group-containing (meth)acrylic resin can be exemplified by 38 mole% and 35 mole %, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 2.5 mol%, etc., the lower limit can be exemplified by 35 mol%, 30 mol% , 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 2.5 mol%, 1.5 mol%, etc. In one embodiment, the content range of the constituent units derived from the hydroxyl group-containing (meth)acrylic acid alkyl ester in 100 mole% of all the constituent units of the hydroxyl group-containing (meth)acrylic resin is desirably about 1.5 mole% to 38 mole%.

源自含羥基的(甲基)丙烯酸烷酯的構成單元在含羥基的(甲基)丙烯酸樹脂的全部構成單元100質量%中所占的含量的上限可例示35質量%、30質量%、25質量%、20質量%、15質量%、10質量%、5質量%、2.5質量%等,下限可例示30質量%、25質量%、20質量%、15質量%、10質量%、5質量%、2.5質量%、2質量%等。在一個實施型態中,源自含羥基的(甲 基)丙烯酸烷酯的構成單元在含羥基的(甲基)丙烯酸樹脂的全部構成單元100質量%中所占的含量的範圍理想為約2質量%~35質量%。 The upper limit of the content of the constituent units derived from the hydroxyl group-containing (meth)acrylic acid alkyl ester in 100% by mass of all the constituent units of the hydroxyl group-containing (meth)acrylic resin can be exemplified by 35% by mass, 30% by mass, and 25 Mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 2.5 mass%, etc., the lower limit can be exemplified by 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass% , 2.5% by mass, 2% by mass, etc. In one embodiment, the content range of the structural units derived from the hydroxyl group-containing (meth)acrylic acid alkyl ester in 100% by mass of all the structural units of the hydroxyl group-containing (meth)acrylic resin is desirably about 2 Mass%~35 mass%.

含羥基的(甲基)丙烯酸樹脂中的源自不含羥基的(甲基)丙烯酸烷酯的構成單元與源自含羥基的(甲基)丙烯酸烷酯的構成單元的物質的量之比(不含羥基的(甲基)丙烯酸烷酯mol/含羥基的(甲基)丙烯酸烷酯mol)的上限可例示57、50、40、30、20、15、10、5、2等,下限可例示55、50、40、30、20、15、10、5、2、1.6等。在一個實施型態中,含羥基的(甲基)丙烯酸樹脂中的源自不含羥基的(甲基)丙烯酸烷酯的構成單元與源自含羥基的(甲基)丙烯酸烷酯的構成單元的物質的量之比(不含羥基的(甲基)丙烯酸烷酯mol/含羥基的(甲基)丙烯酸烷酯mol)理想為約1.6~57,更理想為5~15。 Ratio of the amount of the constituent unit derived from the (meth)acrylic acid alkyl group not containing a hydroxyl group to the constituent unit derived from the (meth)acrylic acid alkyl group containing a hydroxyl group in the (meth)acrylic resin containing a hydroxyl group ( The upper limit of hydroxy-free (meth)acrylic acid alkyl ester mol /hydroxy-containing (meth)acrylic acid alkyl ester mol ) can be exemplified by 57, 50, 40, 30, 20, 15, 10, 5, 2, etc., the lower limit can be Examples 55, 50, 40, 30, 20, 15, 10, 5, 2, 1.6, etc. In one embodiment, in the hydroxyl-containing (meth)acrylic resin, the structural unit derived from the non-hydroxyl-containing (meth)acrylic acid alkyl ester and the structural unit derived from the hydroxyl-containing (meth)acrylic acid alkyl ester ratio (no hydroxyl (meth) acrylic acid alkyl ester mol / hydroxyl group-containing (meth) acrylic acid alkyl ester mol) amount of a substance over about 1.6 to 57, more preferably from 5 to 15.

含羥基的(甲基)丙烯酸樹脂中的源自不含羥基的(甲基)丙烯酸烷酯的構成單元與源自含羥基的(甲基)丙烯酸烷酯的構成單元的質量比(不含羥基的(甲基)丙烯酸烷酯mass/含羥基的(甲基)丙烯酸烷酯mass)的上限可例示49、40、30、20、15、10、5、2等,下限可例示45、40、30、20、15、10、5、2、1.8等。在一個實施型態中,含羥基的(甲基)丙烯酸樹脂中的源自不含羥基的(甲基)丙烯酸烷酯的構成單元與源自含羥基的(甲基)丙烯酸烷酯的構成單元的質量比(不含羥基的(甲基)丙烯酸烷酯mass/含羥基的(甲基)丙烯酸烷酯mass),理想為約1.8~49,更理想為5~15。 Mass ratio of the structural unit derived from the (meth)acrylic acid alkyl group which does not contain a hydroxyl group to the structural unit derived from the (meth)acrylic acid alkyl group which contains a hydroxyl group (hydroxyl group-free) the upper limit of the (meth) acrylic acid alkyl ester mass / hydroxyl group-containing (meth) acrylic acid alkyl ester Mass) 49,40,30,20,15,10,5,2 the like may be exemplified, lower limit can be exemplified 45,40, 30, 20, 15, 10, 5, 2, 1.8 etc. In one embodiment, in the hydroxyl-containing (meth)acrylic resin, the structural unit derived from the non-hydroxyl-containing (meth)acrylic acid alkyl ester and the structural unit derived from the hydroxyl-containing (meth)acrylic acid alkyl ester mass ratio (no hydroxyl (meth) acrylic acid alkyl ester mass / hydroxyl group-containing (meth) acrylic acid alkyl ester mass), desirably from about 1.8 to 49, more preferably from 5 to 15.

(不含羥基的(甲基)丙烯酸烷酯及含羥基的(甲基)丙烯酸烷酯以外的單體:亦稱為其他單體) (Monomers other than hydroxyl-free alkyl (meth)acrylate and hydroxyl-containing alkyl (meth)acrylate: also known as other monomers)

製造含羥基的(甲基)丙烯酸樹脂時,亦可以使用不屬於不含羥基的(甲基)丙烯酸烷酯及含羥基的(甲基)丙烯酸烷酯中的任一者的單體。其他單體 亦可以組合使用兩種以上。 When producing a hydroxyl-containing (meth)acrylic resin, a monomer that does not belong to any of the hydroxyl-free alkyl (meth)acrylate and the hydroxyl-containing alkyl (meth)acrylate may also be used. Two or more monomers may be used in combination.

其他單體,可例示(甲基)丙烯酸、α,β-不飽和羧酸、苯乙烯類、α-烯烴、不飽和醇及其等之鹽、二烷基胺基烷基(甲基)丙烯醯胺及其等之鹽、鏈轉移性單體、(甲基)丙烯腈、(甲基)丙烯醯胺類、乙烯胺、雙(甲基)丙烯醯胺、二(甲基)丙烯酸酯、二乙烯酯、上述以外的二官能性單體、三官能性單體、四官能性單體等。 Other monomers can be exemplified by (meth)acrylic acid, α,β-unsaturated carboxylic acids, styrenes, α-olefins, unsaturated alcohols and their salts, dialkylaminoalkyl (meth)propene Acetamide and its salts, chain transfer monomers, (meth)acrylonitrile, (meth)acrylamides, vinylamine, bis(meth)acrylamide, di(meth)acrylate, Divinyl ester, difunctional monomers other than the above, trifunctional monomers, tetrafunctional monomers, etc.

源自其他單體的構成單元在含羥基的(甲基)丙烯酸樹脂的全部構成單元100莫耳%中所占的含量的上限可例示13莫耳%、10莫耳%、9莫耳%、5莫耳%、4莫耳%、1莫耳%等,下限可例示12莫耳%、10莫耳%、9莫耳%、5莫耳%、4莫耳%、1莫耳%、0莫耳%等。在一個實施型態中,源自其他單體的構成單元在含羥基的(甲基)丙烯酸樹脂的全部構成單元100莫耳%中所占的含量的範圍理想為約0莫耳%~13莫耳%。 The upper limit of the content of the structural units derived from other monomers in 100 mol% of all the structural units of the hydroxyl-containing (meth)acrylic resin can be exemplified by 13 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 1 mol%, etc., the lower limit can be exemplified by 12 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 1 mol%, 0 Moore% etc. In one embodiment, the content range of the structural units derived from other monomers in 100 mol% of all the structural units of the (meth)acrylic resin containing hydroxyl groups is desirably about 0 mol% to 13 mol ear%.

源自其他單體的構成單元在含羥基的(甲基)丙烯酸樹脂的全部構成單元100質量%中所占的含量的上限可例示10質量%、9質量%、5質量%、4質量%、1質量%等,下限可例示9質量%、5質量%、4質量%、1質量%、0質量%等。在一個實施型態中,源自其他單體的構成單元在含羥基的(甲基)丙烯酸樹脂的全部構成單元100質量%中所占的含量的範圍理想為約0質量%~10質量%。 The upper limit of the content of constituent units derived from other monomers in 100% by mass of all constituent units of the hydroxyl-containing (meth)acrylic resin can be exemplified by 10% by mass, 9% by mass, 5% by mass, 4% by mass, 1% by mass, etc., the lower limit can be exemplified by 9% by mass, 5% by mass, 4% by mass, 1% by mass, 0% by mass, etc. In one embodiment, the content range of the constituent units derived from other monomers in 100% by mass of all the constituent units of the hydroxyl-containing (meth)acrylic resin is desirably about 0% by mass to 10% by mass.

含羥基的(甲基)丙烯酸樹脂中的源自其他單體的構成單元與源自不含羥基的(甲基)丙烯酸烷酯的構成單元的物質的量之比(其他單體mol/不含羥基的(甲基)丙烯酸烷酯mol)的上限可例示0.22、0.20、0.15、0.10、0.05等,下限可例示0.20、0.15、0.10、0.05、0等。在一個實施型態中,含羥 基的(甲基)丙烯酸樹脂中的源自其他單體的構成單元與源自不含羥基的(甲基)丙烯酸烷酯的構成單元的物質的量之比(其他單體mol/不含羥基的(甲基)丙烯酸烷酯mol)理想為約0~0.22。 Ratio of the amount of the constituent unit derived from other monomers to the constituent unit derived from the (meth)acrylic acid alkyl group not containing hydroxyl groups in the hydroxyl-containing (meth)acrylic resin (other monomers mol /excluded) The upper limit of the hydroxyl (alkyl) (meth)acrylate ( mol ) can be exemplified by 0.22, 0.20, 0.15, 0.10, 0.05, etc., and the lower limit can be exemplified by 0.20, 0.15, 0.10, 0.05, 0, etc. In one embodiment, the ratio of the amounts of the constituent units derived from other monomers to the constituent units derived from the (meth)acrylic acid alkyl group not containing hydroxyl groups in the hydroxyl-containing (meth)acrylic resin ( The other monomer mol /hydroxy-free alkyl (meth)acrylate mol ) is ideally about 0~0.22.

含羥基的(甲基)丙烯酸樹脂中的源自其他單體的構成單元與源自不含羥基的(甲基)丙烯酸烷酯的構成單元的質量比(其他單體mass/不含羥基的(甲基)丙烯酸烷酯mass)的上限可例示0.19、0.15、0.10、0.05等,下限可例示0.15、0.10、0.05、0等。在一個實施型態中,含羥基的(甲基)丙烯酸樹脂中的源自其他單體的構成單元與源自不含羥基的(甲基)丙烯酸烷酯的構成單元的質量比(其他單體mass/不含羥基的(甲基)丙烯酸烷酯mass)理想為約0~0.19。 Mass ratio of structural units derived from other monomers to structural units derived from (meth)acrylic acid alkyl groups not containing hydroxyl groups in (meth)acrylic resins containing hydroxyl groups (other monomer mass /hydroxyl group-free ( The upper limit of the alkyl meth) acrylate mass ) can be exemplified by 0.19, 0.15, 0.10, 0.05, etc., and the lower limit can be exemplified by 0.15, 0.10, 0.05, 0, etc. In one embodiment, the mass ratio of structural units derived from other monomers in the hydroxyl-containing (meth)acrylic resin to structural units derived from alkyl (meth)acrylates not containing hydroxyl groups (other monomers) mass /hydroxy-free (meth)acrylate ( mass ) is ideally about 0~0.19.

含羥基的(甲基)丙烯酸樹脂中的源自其他單體的構成單元與源自含羥基的(甲基)丙烯酸烷酯的構成單元的物質的量之比(其他單體mol/含羥基的(甲基)丙烯酸烷酯mol)的上限可例示8.0、7.0、6.0、5.0、4.0、3.0、2.0、1.0、0.5等,下限可例示7.5、7.0、6.0、5.0、4.0、3.0、2.0、1.0、0.5、0等。在一個實施型態中,含羥基的(甲基)丙烯酸樹脂中的源自其他單體的構成單元與源自含羥基的(甲基)丙烯酸烷酯的構成單元的物質的量之比(其他單體mol/含羥基的(甲基)丙烯酸烷酯mol)理想為約0~8.0。 The ratio of the amount of the constituent unit derived from other monomers to the constituent unit derived from the hydroxyl-containing (meth)acrylic acid resin in the hydroxyl-containing (meth)acrylic resin (other monomer mol / hydroxyl-containing The upper limit of (meth)acrylic acid mol ) can be exemplified by 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0, 0.5, etc., and the lower limit can be exemplified by 7.5, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0 , 0.5, 0, etc. In one embodiment, the ratio of the amount of substances derived from the constituent units of other monomers in the hydroxyl-containing (meth)acrylic resin to the constituent units derived from the hydroxyl-containing (meth)acrylic acid alkyl ester (other The monomer mol /hydroxy-containing alkyl (meth)acrylate mol ) is ideally about 0 to 8.0.

含羥基的(甲基)丙烯酸樹脂中的源自其他單體的構成單元與源自含羥基的(甲基)丙烯酸烷酯的構成單元的質量比(其他單體mass/含羥基的(甲基)丙烯酸烷酯mass)的上限可例示5.0、4.0、3.0、2.0、1.0、0.5等,下限可例示4.5、4.0、3.0、2.0、1.0、0.5、0等。在一個實施型態中,含羥基的(甲基)丙烯酸樹脂中的源自其他單體的構成單元與源自含羥基的(甲基)丙烯 酸烷酯的構成單元的質量比(其他單體mass/含羥基的(甲基)丙烯酸烷酯mass)理想為約0~5.0。 Mass ratio of structural units derived from other monomers in hydroxyl-containing (meth)acrylic resin to structural units derived from hydroxyl-containing (meth)acrylic acid alkyl ester (other monomer mass / hydroxyl-containing (methyl ) The upper limit of alkyl acrylate mass ) can be exemplified by 5.0, 4.0, 3.0, 2.0, 1.0, 0.5, etc., and the lower limit can be exemplified by 4.5, 4.0, 3.0, 2.0, 1.0, 0.5, 0, etc. In one embodiment, the mass ratio of the structural unit derived from other monomers to the structural unit derived from hydroxyl-containing (meth)acrylic acid in the hydroxyl-containing (meth)acrylic resin (other monomer mass / (Hydroxyl-containing (meth) acrylate ( mass )) is ideally about 0 to 5.0.

在一個實施型態中,作為含羥基的(甲基)丙烯酸樹脂,從自我修復性及防污性的觀點出發,理想為含有含羥基的單體及不含羥基的單體的樹脂,更理想為含有含羥基的單體的樹脂。此外,在一個實施型態中,含羥基的(甲基)丙烯酸樹脂理想為含有選自(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯中的一種以上及(甲基)丙烯酸2-羥乙酯的樹脂。 In one embodiment, as the hydroxyl group-containing (meth)acrylic resin, from the viewpoint of self-healing and antifouling properties, it is preferably a resin containing a hydroxyl group-containing monomer and a hydroxyl group-free monomer, more preferably It is a resin containing hydroxyl-containing monomers. In addition, in one embodiment, the hydroxyl-containing (meth)acrylic resin preferably contains one or more kinds selected from methyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylic acid 2- Hydroxyethyl resin.

<含羥基的(甲基)丙烯酸樹脂的物性等> <Physical properties of hydroxyl-containing (meth)acrylic resin, etc.>

含羥基的(甲基)丙烯酸樹脂的玻璃轉變溫度的上限可例示100℃、90℃、80℃、70℃、60℃等,下限可例示90℃、80℃、70℃、60℃、50℃、40℃等。在一個實施型態中,從薄膜、硬化物的加工性優良的觀點出發,含羥基的(甲基)丙烯酸樹脂的玻璃轉變溫度理想為40~100℃。此外,在一個實施型態中,從薄膜、硬化物的自我修復性及加工性此二者特別優良的觀點出發,含羥基的(甲基)丙烯酸樹脂的玻璃轉變溫度理想為40~90℃,更理想為40~80℃,進一步更理想為40~70℃,特別理想為50~70℃,進一步特別理想為50~60℃。 The upper limit of the glass transition temperature of the hydroxyl group-containing (meth)acrylic resin can be exemplified by 100°C, 90°C, 80°C, 70°C, 60°C, etc., and the lower limit can be exemplified by 90°C, 80°C, 70°C, 60°C, 50°C , 40 ℃ and so on. In one embodiment, the glass transition temperature of the hydroxyl group-containing (meth)acrylic resin is preferably from 40 to 100°C from the viewpoint of excellent processability of the film and cured product. In addition, in one embodiment, the glass transition temperature of the hydroxyl-containing (meth)acrylic resin is ideally 40 to 90°C from the viewpoint that both the self-healing properties and the workability of the film and the cured product are particularly excellent. More desirably 40 to 80°C, further more desirably 40 to 70°C, particularly desirably 50 to 70°C, even more desirably 50 to 60°C.

玻璃轉變溫度藉由Fox公式算出。 The glass transition temperature is calculated by the Fox formula.

Fox公式:1/Tg=(Wa/Tga)+(Wb/Tgb)+...+(Wn/Tgn) Fox formula: 1/Tg=(Wa/Tga)+(Wb/Tgb)+...+(Wn/Tgn)

Tg:共聚物的玻璃轉變溫度(K) Tg: glass transition temperature of the copolymer (K)

Wa:單體A的質量% Wa: Mass% of monomer A

Tga:單體A的均聚物的玻璃轉變溫度(K) Tga: Glass transition temperature of homopolymer of monomer A (K)

Wb:單體B的質量% Wb: mass% of monomer B

Tgb:單體B的均聚物的玻璃轉變溫度(K) Tgb: glass transition temperature of homopolymer of monomer B (K)

Wn:單體N的質量% Wn: mass% of monomer N

Tgn:單體N的均聚物的玻璃轉變溫度(K) Tgn: glass transition temperature of homopolymer of monomer N (K)

含羥基的(甲基)丙烯酸樹脂的羥基當量的上限可例示2.7meq/g、2.5meq/g、2.0meq/g、1.8meq/g、1.5meq/g、1.0meq/g、0.5meq/g、0.25meq/g等,下限可例示2.5meq/g、2.0meq/g、1.8meq/g、1.5meq/g、1.0meq/g、0.5meq/g、0.25meq/g、0.17meq/g等。在一個實施型態中,含羥基的(甲基)丙烯酸樹脂的羥基當量理想為約0.17meq/g~2.7meq/g,更理想為約0.5meq/g~1.8meq/g。 The upper limit of the hydroxyl equivalent of the hydroxyl group-containing (meth)acrylic resin can be exemplified by 2.7meq/g, 2.5meq/g, 2.0meq/g, 1.8meq/g, 1.5meq/g, 1.0meq/g, 0.5meq/g , 0.25meq/g, etc., the lower limit can be exemplified 2.5meq/g, 2.0meq/g, 1.8meq/g, 1.5meq/g, 1.0meq/g, 0.5meq/g, 0.25meq/g, 0.17meq/g, etc. . In one embodiment, the hydroxyl equivalent of the hydroxyl-containing (meth)acrylic resin is desirably about 0.17 meq/g to 2.7 meq/g, and more desirably about 0.5 meq/g to 1.8 meq/g.

在本發明中,羥基當量為在固體1g中所存在的羥基的物質的量。 In the present invention, the hydroxyl equivalent is the amount of the hydroxyl group present in 1 g of the solid.

含羥基的(甲基)丙烯酸樹脂的羥值(固體成分換算)的上限可例示150mgKOH/g、140mgKOH/g、130mgKOH/g、120mgKOH/g、110mgKOH/g、100mgKOH/g、90mgKOH/g、80mgKOH/g、70mgKOH/g、60mgKOH/g、50mgKOH/g、40mgKOH/g、30mgKOH/g、20mgKOH/g、15mgKOH/g等,下限可例示140mgKOH/g、130mgKOH/g、120mgKOH/g、110mgKOH/g、100mgKOH/g、90mgKOH/g、80mgKOH/g、70mgKOH/g、60mgKOH/g、50mgKOH/g、40mgKOH/g、30mgKOH/g、20mgKOH/g、15mgKOH/g、10mgKOH/g等。在一個實施型態中,含羥基的(甲基)丙烯酸樹脂的羥值(固體成分換算)理想為約10mgKOH/g~150mgKOH/g,更理想為40~100mgKOH/g,進一步更理想為40~90mgKOH/g,特別理想為40~80mgKOH/g,進一步特別理想為40~70mgKOH/g,最理想為40~60mgKOH/g。 The upper limit of the hydroxyl value (solid content conversion) of the hydroxyl group-containing (meth)acrylic resin can be exemplified by 150mgKOH/g, 140mgKOH/g, 130mgKOH/g, 120mgKOH/g, 110mgKOH/g, 100mgKOH/g, 90mgKOH/g, 80mgKOH /g, 70mgKOH/g, 60mgKOH/g, 50mgKOH/g, 40mgKOH/g, 30mgKOH/g, 20mgKOH/g, 15mgKOH/g, etc., the lower limit can be exemplified by 140mgKOH/g, 130mgKOH/g, 120mgKOH/g, 110mgKOH/g , 100mgKOH/g, 90mgKOH/g, 80mgKOH/g, 70mgKOH/g, 60mgKOH/g, 50mgKOH/g, 40mgKOH/g, 30mgKOH/g, 20mgKOH/g, 15mgKOH/g, 10mgKOH/g, etc. In one embodiment, the hydroxyl value (solid content conversion) of the hydroxyl-containing (meth)acrylic resin is preferably about 10 mgKOH/g~150 mgKOH/g, more preferably 40-100 mgKOH/g, and even more preferably 40~ 90mgKOH/g, particularly ideal is 40~80mgKOH/g, further particularly ideal is 40~70mgKOH/g, most ideal is 40~60mgKOH/g.

羥值依據JIS K1557-1藉由乙醯化法進行測定。 The hydroxyl value is measured by the acetylation method according to JIS K1557-1.

含羥基的(甲基)丙烯酸樹脂的重均分子量(Mw)的上限可例示100000、90000、80000、70000、60000、50000、40000、30000、20000、10000、5000、4000等,下限可例示90000、80000、70000、60000、50000、40000、30000、20000、10000、5000、4000、3000等。在一個實施型態中,從自我修復性塗覆劑的抗結塊性、初始密著性及耐濕熱密著性的觀點出發,含羥基的(甲基)丙烯酸樹脂的重均分子量(Mw)理想為約3000~100000,更理想為約10000~80000。 The upper limit of the weight-average molecular weight (Mw) of the hydroxyl-containing (meth)acrylic resin can be exemplified by 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30000, 20000, 10000, 5000, 4000, etc., and the lower limit can be exemplified by 90,000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, 3000, etc. In one embodiment, the weight-average molecular weight (Mw) of the hydroxyl-containing (meth)acrylic resin is considered from the viewpoints of the blocking resistance, initial adhesion, and moisture and heat resistance of the self-healing coating agent. Ideally, it is about 3,000 to 100,000, and more preferably about 10,000 to 80,000.

含羥基的(甲基)丙烯酸樹脂的數均分子量(Mn)的上限可例示100000、90000、80000、70000、60000、50000、40000、30000、20000、10000、5000、4000等,下限可例示90000、80000、70000、60000、50000、40000、30000、20000、10000、5000、4000、3000等。在一個實施型態中,從自我修復性塗覆劑的抗結塊性、初始密著性及耐濕熱密著性的觀點出發,含羥基的(甲基)丙烯酸樹脂的數均分子量(Mn)理想為約3000~100000,更理想為約10000~80000。 The upper limit of the number average molecular weight (Mn) of the hydroxyl-containing (meth)acrylic resin can be exemplified by 100,000, 90,000, 80000, 70000, 60000, 50,000, 40,000, 30000, 20,000, 10000, 5000, 4000, etc., and the lower limit can be exemplified by 90,000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, 4000, 3000, etc. In one embodiment, the number-average molecular weight (Mn) of the hydroxyl-containing (meth)acrylic resin is from the viewpoint of the blocking resistance, initial adhesion and moisture-heat adhesion of the self-healing coating agent Ideally, it is about 3,000 to 100,000, and more preferably about 10,000 to 80,000.

在本發明中,重均分子量及數均分子量是藉由凝膠滲透層析(GPC)作為在適當的溶劑中測定的聚苯乙烯換算值而測定。 In the present invention, the weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC) as a polystyrene conversion value measured in an appropriate solvent.

含羥基的(甲基)丙烯酸樹脂的分子量分布(Mw/Mn)的上限可例示10、7.5、5、2.5、2等,下限可例示9.5、7.5、5、2.5、2、1.5等。在一個實施型態中,含羥基的(甲基)丙烯酸樹脂的分子量分布(Mw/Mn)理想為約1.5~10。 The upper limit of the molecular weight distribution (Mw/Mn) of the hydroxyl group-containing (meth)acrylic resin can be exemplified by 10, 7.5, 5, 2.5, 2, etc., and the lower limit can be exemplified by 9.5, 7.5, 5, 2.5, 2, 1.5, etc. In one embodiment, the molecular weight distribution (Mw/Mn) of the hydroxyl-containing (meth)acrylic resin is ideally about 1.5-10.

含羥基的(甲基)丙烯酸樹脂可藉由各種習知的方法製造。含 羥基的(甲基)丙烯酸樹脂的製造方法可例示:使不含羥基的(甲基)丙烯酸烷酯及含羥基的(甲基)丙烯酸烷酯、以及根據需要的其他單體,在無溶劑下或有機溶劑中,通常在聚合引發劑的存在下在約80℃~180℃下進行約1小時~10小時的共聚反應的方法等。製造含羥基的(甲基)丙烯酸樹脂時使用的有機溶劑及聚合引發劑,可例示各種習知的有機溶劑及聚合引發劑、及/或後述的有機溶劑及聚合引發劑等。 The hydroxyl-containing (meth)acrylic resin can be produced by various conventional methods. An example of a method for producing a hydroxyl-containing (meth)acrylic resin is to use a non-hydroxyl-containing (meth)acrylic acid alkyl ester, a hydroxyl-containing (meth)acrylic acid alkyl ester, and other monomers as needed in a solvent-free In a low temperature or organic solvent, a method of performing a copolymerization reaction at about 80° C. to 180° C. for about 1 hour to 10 hours in the presence of a polymerization initiator is generally used. Examples of organic solvents and polymerization initiators used when producing hydroxyl-containing (meth)acrylic resins include various conventional organic solvents and polymerization initiators, and/or organic solvents and polymerization initiators described below.

在一個實施型態中,自我修復性塗覆劑中的含羥基的(甲基)丙烯酸樹脂的含量,理想為20~70質量%。 In one embodiment, the content of the hydroxyl-containing (meth)acrylic resin in the self-healing coating agent is ideally 20 to 70% by mass.

<含羥基的聚矽氧烷> <Hydroxy-containing polysiloxane>

含羥基的聚矽氧烷可以單獨使用,亦可以組合使用兩種以上。在本發明中,含羥基的聚矽氧烷是指在分子內具有羥基且具有矽氧烷鍵的主鏈的聚合物。含羥基的聚矽氧烷,可例示丙烯酸聚合物改性含羥基的聚矽氧烷、聚酯改性含羥基的聚矽氧烷、聚醚改性含羥基的聚矽氧烷、甲醇改性含羥基的聚矽氧烷等有機改性含羥基的聚矽氧烷。又,從反應性良好的觀點出發,羥基理想為包含在改性部位。各種聚矽氧烷中藉由使用含羥基的聚矽氧烷,本發明的自我修復性塗覆劑硬化而得到的硬化物、薄膜的透明性優良。 The hydroxyl-containing polysiloxane can be used alone or in combination of two or more. In the present invention, the hydroxyl-containing polysiloxane refers to a polymer having a hydroxyl group in the molecule and a main chain having a siloxane bond. Hydroxy-containing polysiloxane, exemplified by acrylic polymer modified hydroxyl-containing polysiloxane, polyester modified hydroxyl-containing polysiloxane, polyether modified hydroxyl-containing polysiloxane, methanol modification Hydroxy-containing polysiloxane and other organically modified hydroxyl-containing polysiloxane. In addition, from the viewpoint of good reactivity, the hydroxyl group is preferably included in the modified site. Among various polysiloxanes, by using hydroxyl-containing polysiloxanes, the cured products and films obtained by hardening the self-healing coating agent of the present invention are excellent in transparency.

丙烯酸聚合物改性含羥基的聚矽氧烷的市售品,可例示ZX-028-G(T & K TOKA股份有限公司製造)、BYK-SILCLEAN3700(畢克化學.日本股份有限公司製造)、SYMAC US-270(東亞合成股份有限公司製造)等。 Commercial products of acrylic polymer-modified hydroxyl-containing polysiloxanes can be exemplified by ZX-028-G (manufactured by T & K TOKA Co., Ltd.), BYK-SILCLEAN 3700 (manufactured by BYK Chemical Co., Ltd. of Japan), SYMAC US-270 (manufactured by East Asia Synthetic Co., Ltd.), etc.

聚醚改性含羥基的聚矽氧烷或聚酯改性含羥基的聚矽氧烷的市售品,可例示BYK-370、BYK-375、BYK-377、BYK-SILCLEAN3720(畢克化學.日本股份有限公司製造)、X-22-4952、KF-6123(信越化學工業股份 有限公司製造)等。 Commercial products of polyether-modified hydroxyl-containing polysiloxane or polyester-modified hydroxyl-containing polysiloxane can be exemplified by BYK-370, BYK-375, BYK-377, BYK-SILCLEAN3720 (Bike Chemical. Made in Japan Co., Ltd.), X-22-4952, KF-6123 (made by Shin-Etsu Chemical Industry Co., Ltd.), etc.

甲醇改性含羥基的聚矽氧烷的市售品,可例示X-22-4039、X-22-4015、X-22-4952、X-22-4272、X-22-170BX、X-22-170DX、KF-6000、KF-6001、KF-6002、KF-6003、KF-6123、X-22-176F(信越化學工業股份有限公司製造)、SILAPLANE FM-4411、SILAPLANE FM-4421、SILAPLANE FM-4425、SILAPLANE FM-0411、SILAPLANE FM-0421、SILAPLANE FM-DA11、SILAPLANE FM-DA21、SILAPLANE FM-DA26(JNC股份有限公司製造)等。 Commercial products of methanol-modified hydroxyl-containing polysiloxanes can be exemplified by X-22-4039, X-22-4015, X-22-4952, X-22-4272, X-22-170BX, X-22 -170DX, KF-6000, KF-6001, KF-6002, KF-6003, KF-6123, X-22-176F (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), SILAPLANE FM-4411, SILAPLANE FM-4421, SILAPLANE FM -4425, SILAPLANE FM-0411, SILAPLANE FM-0421, SILAPLANE FM-DA11, SILAPLANE FM-DA21, SILAPLANE FM-DA26 (manufactured by JNC Corporation), etc.

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的聚矽氧烷的含量,理想為1~10質量%。 In one embodiment, the content of the hydroxyl-containing polysiloxane in the self-healing coating agent is ideally 1-10% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的(甲基)丙烯酸樹脂與含羥基的聚矽氧烷的質量比(含羥基的(甲基)丙烯酸樹脂mass/含羥基的聚矽氧烷mass),理想為10~30,更理想為15~25。 In one embodiment, the mass ratio of hydroxyl-containing (meth)acrylic resin to hydroxyl-containing polysiloxane in the self-healing coating agent (hydroxyl-containing (meth)acrylic resin mass /hydroxyl-containing silicon Mass poly siloxane), over 10 to 30, more preferably from 15 to 25.

<多異氰酸酯> <polyisocyanate>

在本發明中,「多異氰酸酯」為具有兩個以上異氰酸酯基(-N=C=O)的化合物。多異氰酸酯,可例示脂肪族多異氰酸酯、芳香族多異氰酸酯等。多異氰酸酯可以單獨使用,亦可以組合使用兩種以上。 In the present invention, "polyisocyanate" is a compound having two or more isocyanate groups (-N=C=O). Examples of the polyisocyanate include aliphatic polyisocyanate and aromatic polyisocyanate. The polyisocyanate may be used alone or in combination of two or more.

脂肪族多異氰酸酯,可例示直鏈脂肪族多異氰酸酯、支鏈脂肪族多異氰酸酯、脂環族多異氰酸酯等。 Examples of the aliphatic polyisocyanate include linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, and alicyclic polyisocyanate.

直鏈脂肪族基團,可例示直鏈亞烷基等。直鏈亞烷基,可以由通式-(CH2)n-(n為1以上的整數)表示,可例示亞甲基、亞乙基、亞丙基、正亞丁基、正亞戊基、正亞己基、正亞庚基、正亞辛基、正亞壬基、正十亞甲 基等。 The straight-chain aliphatic group may, for example, be a straight-chain alkylene group. Linear alkylene group, which can be represented by the general formula -(CH 2 ) n- (n is an integer of 1 or more), exemplified by methylene, ethylene, propylene, n-butylene, n-pentylene, N-hexylene, n-heptylene, n-octylene, n-nonylene, n-decyl methylene, etc.

直鏈脂肪族多異氰酸酯,可例示:亞甲基二異氰酸酯、二亞甲基二異氰酸酯、三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、五亞甲基二異氰酸酯、六亞甲基二異氰酸酯、七亞甲基二異氰酸酯、八亞甲基二異氰酸酯、九亞甲基二異氰酸酯、十亞甲基二異氰酸酯等。 Linear aliphatic polyisocyanate, exemplified by methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, Heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, etc.

支鏈脂肪族基團,可例示支鏈亞烷基等。支鏈亞烷基是直鏈亞烷基的至少一個氫被烷基取代後的基團,具體的例子可例示二乙基亞戊基、三甲基亞丁基、三甲基亞戊基、三甲基亞己基(三甲基六亞甲基)等。 The branched aliphatic group may be exemplified by a branched alkylene group. A branched alkylene group is a group in which at least one hydrogen of a linear alkylene group is substituted with an alkyl group. Specific examples include diethylpentylene, trimethylbutylene, trimethylpentylene, tri Methylhexylene (trimethylhexamethylene), etc.

支鏈脂肪族多異氰酸酯,可例示二乙基亞戊基二異氰酸酯、三甲基亞丁基二異氰酸酯、三甲基亞戊基二異氰酸酯、三甲基六亞甲基二異氰酸酯等。 Examples of branched aliphatic polyisocyanates include diethylpentyl diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

脂環族基團,可例示單環脂環族基團、橋環脂環族基團、稠環脂環族基團等。此外,亞環烷基可以是一個以上的氫被直鏈或支鏈烷基取代。 The alicyclic group may be exemplified by a monocyclic alicyclic group, a bridged alicyclic group, a condensed alicyclic group, and the like. In addition, the cycloalkylene group may be substituted with more than one hydrogen by a linear or branched alkyl group.

在本發明中,單環是指在由碳的共價鍵形成的內部不具有橋聯結構的環狀結構。此外,稠環是指兩個以上單環共有兩個原子(即,使各個環相互僅共有(稠合)一個邊)的環狀結構。橋環是指兩個以上單環共有三個以上原子的環狀結構。 In the present invention, a single ring refers to a ring structure that does not have a bridge structure inside a covalent bond of carbon. In addition, a fused ring refers to a cyclic structure in which two or more single rings share two atoms (that is, each ring shares (fused) only one side with each other). A bridge ring refers to a ring structure in which more than two single rings share more than three atoms.

單環脂環族基團,可例示亞環戊基、亞環己基、亞環庚基、亞環癸基、3,5,5-三甲基亞環己基等。 The monocyclic alicyclic group may be exemplified by cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, 3,5,5-trimethylcyclohexylene, and the like.

橋環脂環族基團,可例示亞三環癸基、亞金剛烷基、亞降莰基等。 Examples of the bridged alicyclic group include tricyclodecylene, adamantylene, and norbornylene.

稠環脂環族基團,可例示亞雙環癸基等。 Examples of the fused cycloaliphatic group include bicyclodecylene.

脂環族多異氰酸酯,可例示單環脂環族多異氰酸酯、橋環脂環族多異氰酸酯、稠環脂環族多異氰酸酯等。 Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, bridged alicyclic polyisocyanate, and condensed alicyclic polyisocyanate.

單環脂環族多異氰酸酯,可例示:氫化苯二亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、亞環戊基二異氰酸酯、亞環己基二異氰酸酯、亞環庚基二異氰酸酯、亞環癸基二異氰酸酯、3,5,5-三甲基亞環己基二異氰酸酯、二環己基甲烷二異氰酸酯等。 Monocyclic alicyclic polyisocyanate, exemplified by hydrogenated xylylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptyl diisocyanate, cyclodecene Diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, etc.

橋環脂環族多異氰酸酯,可例示亞三環癸基二異氰酸酯、金剛烷二異氰酸酯、降莰烯二異氰酸酯等。 Examples of bridged cycloaliphatic polyisocyanates include tricyclodecyl diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like.

稠環脂環族多異氰酸酯,可例示亞雙環癸基二異氰酸酯等。 Examples of the fused cycloaliphatic polyisocyanate include bicyclodecyl diisocyanate.

脂肪族基團的碳原子數並無特別限定,其上限可例示30、29、25、20、16、12、10、9、8、7、6、5、4、3、2等,下限可例示29、25、20、16、12、10、9、8、7、6、5、4、3、2、1等。在一個實施型態中,脂肪族基團的碳原子數理想為1~30,更理想為1~20,進一步理想為1~16,特別理想為1~12。 The number of carbon atoms of the aliphatic group is not particularly limited, and the upper limit may be exemplified by 30, 29, 25, 20, 16, 12, 10, 9, 8, 7, 7, 6, 5, 4, 3, 2, etc., the lower limit may be Examples are 29, 25, 20, 16, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc. In one embodiment, the number of carbon atoms of the aliphatic group is desirably 1-30, more desirably 1-20, further desirably 1-16, and particularly desirably 1-12.

芳香族基團,可例示亞苯基、亞萘基等。 Examples of the aromatic group include phenylene and naphthylene.

芳香族多異氰酸酯,可例示甲苯二異氰酸酯、苯二亞甲基二異氰酸酯等。 Examples of the aromatic polyisocyanate include toluene diisocyanate and xylylene diisocyanate.

在一個實施型態中,多異氰酸酯中,從耐候性及自我修復性的觀點出發,理想為脂肪族多異氰酸酯,更理想為直鏈脂肪族多異氰酸酯。 In one embodiment, the polyisocyanate is preferably an aliphatic polyisocyanate from the viewpoint of weather resistance and self-healing properties, and more preferably a linear aliphatic polyisocyanate.

在一個實施型態中,多異氰酸酯的NCO含有率(NCO%)理想為5~30質量%。 In one embodiment, the NCO content (NCO%) of the polyisocyanate is ideally 5-30% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的多異氰酸酯的含量理想為5~50質量%。 In one embodiment, the content of the polyisocyanate in the self-healing coating agent is desirably 5 to 50% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的選自由含羥基的(甲基)丙烯酸樹脂、及含羥基的聚矽氧烷所成群中的一種以上的總含量與多異氰酸酯的質量比(選自由含羥基的(甲基)丙烯酸樹脂、及含羥基的聚矽氧烷所成群中的一種以上的總含量maas/多異氰酸酯mass)理想為1/0.2~1/20。 In one embodiment, the total content of one or more of the self-healing coating agents selected from the group consisting of hydroxyl-containing (meth)acrylic resins and hydroxyl-containing polysiloxanes and polyisocyanates mass ratio of (total content maas resin, hydroxyl group-containing poly-silicon and siloxane groups in the one or more selected from the group consisting of hydroxyl group-containing (meth) acrylate / polyisocyanate mass) over 1 / 0.2 to 1/20.

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的(甲基)丙烯酸樹脂與多異氰酸酯的質量比(含羥基的(甲基)丙烯酸樹脂mass/多異氰酸酯mass)理想為1/0.25~1/2.4。 In one embodiment, the mass ratio of hydroxyl-containing (meth)acrylic resin to polyisocyanate (hydroxyl-containing (meth)acrylic resin mass /polyisocyanate mass ) in the above-mentioned self-healing coating agent is ideally 1 /0.25~1/2.4.

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的聚矽氧烷與多異氰酸酯的質量比(含羥基的聚矽氧烷mass/多異氰酸酯mass)理想為0.01/1~0.2/1。 In one embodiment, the mass ratio of hydroxyl-containing polysiloxane to polyisocyanate (hydroxyl-containing polysiloxane mass /polyisocyanate mass ) in the above-mentioned self-healing coating agent is preferably 0.01/1 to 0.2 /1.

在一個實施型態中,特別是由於防污性及加工性兩方面優良,因此,上述自我修復性塗覆劑中的多異氰酸酯,理想為包含選自多異氰酸酯的加成物、多異氰酸酯的脲基甲酸酯體、多異氰酸酯的縮二脲體及多異氰酸酯的異氰脲酸酯體中的兩種以上;更理想為包含多異氰酸酯的加成物及多異氰酸酯的異氰脲酸酯體、多異氰酸酯的脲基甲酸酯體及多異氰酸酯的縮二脲體、或者多異氰酸酯的加成物及多異氰酸酯的縮二脲體。此等組合中,從防污性及加工性兩方面特別優良的觀點出發,最理想為包含多異氰酸酯的加成物及多異氰酸酯的縮二脲體。 In one embodiment, the polyisocyanate in the above-mentioned self-healing coating agent is desirably an urea containing an adduct selected from polyisocyanate and a polyisocyanate, because of its excellent antifouling properties and processability. Two or more of carbamate body, polyisocyanate biuret body and polyisocyanate isocyanurate body; more preferably, polyisocyanate adducts and polyisocyanate isocyanurate body, Polyisocyanate allophanate body and polyisocyanate biuret body, or polyisocyanate adduct and polyisocyanate biuret body. Among these combinations, from the viewpoint of being particularly excellent in both antifouling properties and processability, it is most desirable to include a polyisocyanate adduct and a polyisocyanate biuret.

在一個實施型態中,在上述自我修復性塗覆劑中含有兩種多異氰酸酯的情況下,兩種多異氰酸酯的總含量100質量%中,各多異氰酸酯 的含量理想為20~80質量%,更理想為30~80質量%,進一步更理想為30~70質量%,特別理想為35~70質量%,進一步特別理想為35~65質量%,最理想為40~60質量%。在兩種多異氰酸酯為上述範圍內的情況下,與處於範圍外的情況相比,自我修復性、加工性變得更加良好。 In one embodiment, in the case where the above-mentioned self-healing coating agent contains two polyisocyanates, the total content of the two polyisocyanates is 100% by mass, and the content of each polyisocyanate is ideally 20 to 80% by mass. It is more preferably 30 to 80% by mass, further more preferably 30 to 70% by mass, particularly ideal 35 to 70% by mass, further particularly ideal 35 to 65% by mass, and most preferably 40 to 60% by mass. When the two kinds of polyisocyanates are within the above-mentioned range, the self-healing property and processability become better than those outside the range.

在一個實施型態中,在上述自我修復性塗覆劑中含有兩種多異氰酸酯的情況下,兩種多異氰酸酯的質量比(一種多異氰酸酯mass/另一種多異氰酸酯mass)理想為0.1~5,更理想為0.5~3,進一步更理想為0.7~2。在兩種多異氰酸酯為上述範圍內的情況下,與處於範圍外的情況相比,自我修復性、加工性變得更加良好。 In one embodiment, when the above-mentioned self-healing coating agent contains two polyisocyanates, the mass ratio of the two polyisocyanates (one polyisocyanate mass /another polyisocyanate mass ) is ideally 0.1 to 5, More preferably, it is 0.5~3, and further more preferably, it is 0.7~2. When the two kinds of polyisocyanates are within the above-mentioned range, the self-healing property and processability become better than those outside the range.

<多異氰酸酯的加成物> <adduct of polyisocyanate>

多異氰酸酯的加成物可以單獨使用,亦可以組合使用兩種以上。製造多異氰酸酯的加成物時,多異氰酸酯可以單獨使用,亦可以組合使用兩種以上。多異氰酸酯可例示上述的多異氰酸酯等。 The polyisocyanate adduct may be used alone or in combination of two or more. When manufacturing the polyisocyanate adduct, the polyisocyanate may be used alone or in combination of two or more. The polyisocyanate can be exemplified by the above-mentioned polyisocyanates and the like.

多異氰酸酯的加成物可例示: 下述通式所表示的三羥甲基丙烷與多異氰酸酯的加成物,

Figure 108124543-A0202-12-0020-3
The polyisocyanate adducts can be exemplified: the adducts of trimethylolpropane and polyisocyanate represented by the following general formula,
Figure 108124543-A0202-12-0020-3

(式中,RadA~RadE各自獨立地為亞烷基或亞芳基,RadD~RadE在各個構成單元中基團可以不同。nad為0以上的整數。nad理想為0~3); 下述通式所表示的甘油與多異氰酸酯的加成物,

Figure 108124543-A0202-12-0021-4
(Wherein, R adA ~ R adE are each independently an alkylene group or an arylene group, R adD ~ R adE in the unit constituting the respective groups may be different .n ad is an integer of 0 or more is over 0 ~ .n ad 3); The adduct of glycerin and polyisocyanate represented by the following general formula,
Figure 108124543-A0202-12-0021-4

(式中,Radα~Radε各自獨立地為亞烷基或亞芳基,Radδ~Radε在各個構成單元中基團可以不同。nad1為0以上的整數。nad1理想為0~3)等。 (In the formula, R adα ~ R adε are each independently an alkylene group or an arylene group, and R adδ ~ R adε may be different in each constituent unit. n ad1 is an integer of 0 or more. n ad1 is ideally 0 ~ 3) Wait.

又,上述通式的RadA~RadE及上述通式的Radα~Radε的基團分別可以具有一個以上酯基、醚基或羰基等各種官能團。 And, R adα ~ R adε radicals R adA ~ R adE the above formula and the above formula may have various functional groups are more than one ester group, an ether group or a carbonyl group.

多異氰酸酯的加成物的市售品,可例示:Duranate P301-75E(旭化成股份有限公司製造)、Duranate E402-80B(旭化成股份有限公司製造)、Duranate E405-70B(旭化成股份有限公司製造)、Coronate HL(東曹股份有限公司製造)、Burnock D-750(DIC股份有限公司製造)等。 Commercial products of polyisocyanate adducts can be exemplified: Duranate P301-75E (manufactured by Asahi Kasei Corporation), Duranate E402-80B (manufactured by Asahi Kasei Corporation), Duranate E405-70B (manufactured by Asahi Kasei Corporation), Coronate HL (manufactured by Tosoh Corporation), Burnock D-750 (manufactured by DIC Corporation), etc.

在一個實施型態中,多異氰酸酯的加成物的重均分子量(Mw)理想為1000~4000。 In one embodiment, the weight average molecular weight (Mw) of the polyisocyanate adduct is ideally 1,000 to 4,000.

在一個實施型態中,多異氰酸酯的加成物的數均分子量(Mn)理想為1000~3000。 In one embodiment, the number average molecular weight (Mn) of the polyisocyanate adduct is ideally 1,000 to 3,000.

在一個實施型態中,多異氰酸酯的加成物的分子量分布(Mw/Mn)理想為1.2~1.5。 In one embodiment, the molecular weight distribution (Mw/Mn) of the polyisocyanate adduct is ideally 1.2 to 1.5.

在一個實施型態中,多異氰酸酯的加成物的NCO含有率(NCO%)理想為5~30質量%。 In one embodiment, the NCO content (NCO%) of the polyisocyanate adduct is ideally 5 to 30% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的多異氰酸酯的加成物的含量,理想為1~99質量%。 In one embodiment, the content of the polyisocyanate adduct in the self-healing coating agent is preferably 1 to 99% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的選自由含羥基的(甲基)丙烯酸樹脂、及含羥基的聚矽氧烷所成群中的一種以上的總含量與多異氰酸酯的加成物的質量比(選自由含羥基的(甲基)丙烯酸樹脂、及含羥基的聚矽氧烷所成群中的一種以上的總含量mass/多異氰酸酯的加成物mass)理想為1/0.2~1/20。 In one embodiment, the total content of one or more of the self-healing coating agents selected from the group consisting of hydroxyl-containing (meth)acrylic resins and hydroxyl-containing polysiloxanes and polyisocyanates The mass ratio of the adduct (a total content of more than one mass /polyisocyanate adduct mass selected from the group consisting of hydroxyl-containing (meth)acrylic resin and hydroxyl-containing polysiloxane) is ideally 1 /0.2~1/20.

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的(甲基)丙烯酸樹脂與多異氰酸酯的加成物的質量比(含羥基的(甲基)丙烯酸樹脂mass/多異氰酸酯的加成物mass)理想為1/0.2~1/2。 In one embodiment, the mass ratio of the adduct of hydroxyl-containing (meth)acrylic resin to polyisocyanate in the self-healing coating agent (hydroxyl-containing (meth)acrylic resin mass /polyisocyanate The adduct mass ) is ideally 1/0.2~1/2.

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的聚矽氧烷與多異氰酸酯的加成物的質量比(含羥基的聚矽氧烷mass/多異氰酸酯的加成物mass),理想為0.05~30,更理想為0.05~0.25。 In one embodiment, the mass ratio of the adduct of hydroxyl-containing polysiloxane and polyisocyanate in the self-healing coating agent (hydroxyl-containing polysiloxane mass /polyisocyanate adduct mass ), ideally 0.05 to 30, more preferably 0.05 to 0.25.

<多異氰酸酯的脲基甲酸酯體> <Allophanate body of polyisocyanate>

多異氰酸酯的脲基甲酸酯體可以單獨使用,亦可以組合使用兩種以上。製造多異氰酸酯的脲基甲酸酯體時,多異氰酸酯可以單獨使用,亦可以組合使用兩種以上。多異氰酸酯可例示上述的多異氰酸酯等。 The polyisocyanate allophanate can be used alone or in combination of two or more. When manufacturing the allophanate body of polyisocyanate, the polyisocyanate may be used alone or in combination of two or more. The polyisocyanate can be exemplified by the above-mentioned polyisocyanates and the like.

多異氰酸酯的脲基甲酸酯體可例示下述通式所表示的化合物等。 Examples of the allophanate body of polyisocyanate include compounds represented by the following general formula.

【化5】

Figure 108124543-A0202-12-0023-5
【Chemical 5】
Figure 108124543-A0202-12-0023-5

[式中,nAL為0以上的整數,RALA為烷基或芳基,RALB~RALG各自獨立地為亞烷基或亞芳基,RALα~RALγ各自獨立地為異氰酸酯基或

Figure 108124543-A0202-12-0023-6
[In the formula, n AL is an integer of 0 or more, R ALA is an alkyl group or an aryl group, R ALB to R ALG are each independently an alkylene group or an arylene group, and R ALα to R ALγ are each independently an isocyanate group or
Figure 108124543-A0202-12-0023-6

(nAL1為0以上的整數,RAL1~RAL6各自獨立地為亞烷基或亞芳基,RAL’~RAL'''各自獨立地為異氰酸酯基或RALα~RAlγ本身的基團。 (n AL1 is an integer of 0 or more, R AL1 ~ R AL6 are each independently an alkylene group or an arylene group, and R AL '~R AL ''' are independently an isocyanate group or a group of R ALα ~ R Alγ itself group.

RAL1~RAL4、RAL’~RAL”在各個構成單元中基團可以不同。)。 "R AL1 ~ R AL4 " , R AL '~ R AL " may be different in each constituent unit.).

RALB~RALE、RALα~RALβ在各個構成單元中基團可以不同。] The groups of R ALB ~R ALE and R ALα ~R ALβ may be different in each constituent unit. ]

多異氰酸酯的脲基甲酸酯體的市售品,可例示Takenate D-178N(三井化學股份有限公司製造)、Coronate 2770(東曹股份有限公司製造)、Coronate 2793(東曹股份有限公司製造)、Duranate A201H(旭化成股份 有限公司製造)等。 Commercial products of polyisocyanate allophanate bodies can be exemplified by Takenate D-178N (Mitsui Chemical Co., Ltd.), Coronate 2770 (Tosoh Co., Ltd.), Coronate 2793 (Tosoh Co., Ltd.) , Duranate A201H (made by Asahi Kasei Corporation), etc.

在一個實施型態中,多異氰酸酯的脲基甲酸酯體的重均分子量(Mw)理想為800~3500。 In one embodiment, the weight-average molecular weight (Mw) of the allophanate body of polyisocyanate is ideally 800 to 3500.

在一個實施型態中,多異氰酸酯的脲基甲酸酯體的數均分子量(Mn)理想為700~3000。 In one embodiment, the polyisocyanate allophanate body preferably has a number average molecular weight (Mn) of 700-3000.

在一個實施型態中,多異氰酸酯的脲基甲酸酯體的分子量分布(Mw/Mn)理想為1.0~1.5。 In one embodiment, the molecular weight distribution (Mw/Mn) of the allophanate body of polyisocyanate is ideally 1.0 to 1.5.

多異氰酸酯的脲基甲酸酯體的NCO含有率(NCO%)的上限的例子可以列舉30質量%、25質量%、20質量%、15質量%等,下限的例子可以列舉25質量%、20質量%、15質量%、10質量%、5質量%等。在一個實施型態中,多異氰酸酯的脲基甲酸酯體的NCO含有率(NCO%)理想為5~30質量%。 Examples of the upper limit of the NCO content (NCO%) of the allophanate body of polyisocyanate include 30% by mass, 25% by mass, 20% by mass, and 15% by mass. Examples of the lower limit include 25% by mass and 20% by mass. Mass%, 15 mass%, 10 mass%, 5 mass%, etc. In one embodiment, the NCO content (NCO%) of the allophanate body of polyisocyanate is desirably 5 to 30% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的多異氰酸酯的脲基甲酸酯體的含量,理想為1~99質量%。 In one embodiment, the content of the allophanate body of the polyisocyanate in the self-healing coating agent is preferably 1 to 99% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的選自由含羥基的(甲基)丙烯酸樹脂、及含羥基的聚矽氧烷所成群中的一種以上的總含量與多異氰酸酯的脲基甲酸酯體的質量比(選自由含羥基的(甲基)丙烯酸樹脂、及含羥基的聚矽氧烷所成群中的一種以上的總含量mass/多異氰酸酯的脲基甲酸酯體mass)理想為2/5~15/1。 In one embodiment, the total content of one or more of the self-healing coating agents selected from the group consisting of hydroxyl-containing (meth)acrylic resins and hydroxyl-containing polysiloxanes and polyisocyanates Mass ratio of allophanate body (all selected from the group consisting of hydroxyl-containing (meth)acrylic resin and hydroxyl-containing polysiloxane) total content of mass /polyisocyanate allophanate Body mass ) Ideally 2/5~15/1.

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的(甲基)丙烯酸樹脂與多異氰酸酯的脲基甲酸酯體的質量比(含羥基的(甲基)丙烯酸樹脂mass/多異氰酸酯的脲基甲酸酯體mass)理想為5/1~15/1。 In one embodiment, the mass ratio of the hydroxyl-containing (meth)acrylic resin to the polyisocyanate allophanate body in the self-healing coating agent (hydroxyl-containing (meth)acrylic resin mass / The polyisocyanate allophanate mass ) is ideally 5/1 to 15/1 .

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的聚矽氧烷與多異氰酸酯的脲基甲酸酯體的質量比(含羥基的聚矽氧烷mass/多異氰酸酯的脲基甲酸酯體mass)理想為0.1/1~1/1。 In one embodiment, the mass ratio of the hydroxyl-containing polysiloxane to the polyisocyanate allophanate body in the self-healing coating agent (hydroxyl-containing polysiloxane mass /polyisocyanate urea The carbamate mass ) is ideally 0.1/1 to 1/1.

<多異氰酸酯的縮二脲體> <polyisocyanate biuret>

多異氰酸酯的縮二脲體可以單獨使用,亦可以組合使用兩種以上。製造多異氰酸酯的縮二脲體時,多異氰酸酯可以單獨使用,亦可以組合使用兩種以上。多異氰酸酯可例示上述的多異氰酸酯等。 The polyisocyanate biuret may be used alone or in combination of two or more. In the production of a polyisocyanate biuret, the polyisocyanate may be used alone or in combination of two or more. The polyisocyanate can be exemplified by the above-mentioned polyisocyanates and the like.

多異氰酸酯的縮二脲體可例示下述通式所表示的化合物等。 Examples of the polyisocyanate biuret include compounds represented by the following general formula.

Figure 108124543-A0202-12-0025-7
Figure 108124543-A0202-12-0025-7

[式中,nb為0以上的整數,RbA~RbE各自獨立地為亞烷基或亞芳基,R~R各自獨立地為異氰酸酯基或

Figure 108124543-A0202-12-0025-8
[In the formula, n b is an integer of 0 or more, R bA to R bE are each independently an alkylene group or an arylene group, and R to R are each independently an isocyanate group or
Figure 108124543-A0202-12-0025-8

(nb1為0以上的整數, Rb1~Rb5各自獨立地為亞烷基或亞芳基,Rb’~Rb”各自獨立地為異氰酸酯基或R~R本身的基團。 (n b1 is an integer of 0 or more, R b1 to R b5 are each independently an alkylene group or an arylene group, and R b ′ to R b ”are each independently an isocyanate group or a group of R to R itself.

Rb4~Rb5、Rb”在各個構成單元中基團可以不同。)。 R b4 ~R b5 and R b ”may be different in each constituent unit.).

RbD~RbE、R在各個構成單元中基團可以不同。] The groups of R bD ~R bE and R may be different in each constituent unit. ]

多異氰酸酯的縮二脲體,可例示Duranate 24A-100、Duranate 22A-75P、Duranate 21S-75E(以上為旭化成股份有限公司製造)、Desmodur N3200A(六亞甲基二異氰酸酯的縮二脲體)(以上為住友拜耳聚氨酯股份有限公司製造)等。 Polyisocyanate biuret can be exemplified by Duranate 24A-100, Duranate 22A-75P, Duranate 21S-75E (above manufactured by Asahi Kasei Corporation), Desmodur N3200A (biuret of hexamethylene diisocyanate) ( The above is manufactured by Sumitomo Bayer Polyurethane Co., Ltd.).

在一個實施型態中,多異氰酸酯的縮二脲體的重均分子量(Mw)理想為500~1500。 In one embodiment, the weight average molecular weight (Mw) of the polyisocyanate biuret is ideally 500 to 1500.

在一個實施型態中,多異氰酸酯的縮二脲體的數均分子量(Mn)理想為500~1500。 In one embodiment, the polyisocyanate biuret has a number average molecular weight (Mn) of 500 to 1500.

在一個實施型態中,多異氰酸酯的縮二脲體的分子量分布(Mw/Mn)理想為1.0~1.5。 In one embodiment, the molecular weight distribution (Mw/Mn) of the polyisocyanate biuret is ideally 1.0 to 1.5.

在一個實施型態中,多異氰酸酯的縮二脲體的NCO含有率(NCO%)理想為5~30質量%。 In one embodiment, the polyisocyanate biuret NCO content (NCO%) is desirably 5 to 30% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的多異氰酸酯的縮二脲體的含量,理想為1~99質量%。 In one embodiment, the content of the polyisocyanate biuret in the self-healing coating agent is preferably 1 to 99% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的選自由含羥基的(甲基)丙烯酸樹脂、及含羥基的聚矽氧烷所成群中的一種以上的總含量與多異氰酸酯的縮二脲體的質量比(選自由含羥基的(甲基)丙烯酸樹脂、及含羥基的聚矽氧烷所成群中的一種以上的總含量mass/多異氰酸酯的縮二脲 體mass)理想為1/0.1~1/10。 In one embodiment, the total content of one or more of the self-healing coating agents selected from the group consisting of hydroxyl-containing (meth)acrylic resins and hydroxyl-containing polysiloxanes and polyisocyanates The mass ratio of the biuret body (the total content of more than one mass /polyisocyanate biuret mass selected from the group consisting of (meth)acrylic resins containing hydroxyl groups and polysiloxanes containing hydroxyl groups) is ideal It is 1/0.1~1/10.

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的(甲基)丙烯酸樹脂與多異氰酸酯的縮二脲體的質量比(含羥基的(甲基)丙烯酸樹脂mass/多異氰酸酯的縮二脲體mass)理想為1/0.1~1/2。 In one embodiment, the mass ratio of the hydroxy-containing (meth)acrylic resin to the polyisocyanate biuret in the self-healing coating agent (hydroxyl-containing (meth)acrylic resin mass /polyisocyanate The biuret mass ) is ideally 1/0.1~1/2.

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的聚矽氧烷與多異氰酸酯的縮二脲體的質量比(含羥基的聚矽氧烷mass/多異氰酸酯的縮二脲體mass)理想為0.1/1~0.3/1。 In one embodiment, the mass ratio of the hydroxyl-containing polysiloxane to the polyisocyanate biuret in the self-healing coating agent (hydroxyl-containing polysiloxane mass /polyisocyanate biuret Body mass ) is ideally 0.1/1~0.3/1.

在一個實施型態中,上述自我修復性塗覆劑中的多異氰酸酯的脲基甲酸酯體與多異氰酸酯的縮二脲體的質量比(多異氰酸酯的脲基甲酸酯體mass/多異氰酸酯的縮二脲體mass)理想為1/6~1/1。 In one embodiment, the mass ratio of the polyisocyanate allophanate body to the polyisocyanate biuret body in the above-mentioned self-healing coating agent (polyisocyanate allophanate body mass /polyisocyanate The biuret mass ) is ideally 1/6~1/1.

在一個實施型態中,上述自我修復性塗覆劑中的多異氰酸酯的脲基甲酸酯體、及多異氰酸酯的縮二脲體的總含量,理想為8~25質量%。 In one embodiment, the total content of the polyisocyanate allophanate body and the polyisocyanate biuret body in the self-healing coating agent is preferably 8-25% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的多異氰酸酯的加成物與多異氰酸酯的縮二脲體的質量比(多異氰酸酯的加成物mass/多異氰酸酯的縮二脲體mass)理想為1/6~1/0.5。 In one embodiment, the mass ratio of the polyisocyanate adduct to the polyisocyanate biuret in the self-healing coating agent (polyisocyanate adduct mass /polyisocyanate biuret mass ) Ideally 1/6~1/0.5.

在一個實施型態中,上述自我修復性塗覆劑中的多異氰酸酯的加成物、及多異氰酸酯的縮二脲體的總含量,理想為10~60質量%,更理想為10~35質量%。 In one embodiment, the total content of the polyisocyanate adduct and the polyisocyanate biuret in the self-healing coating agent is preferably 10 to 60% by mass, more preferably 10 to 35% by mass %.

<多異氰酸酯的異氰脲酸酯體> <Isocyanurate body of polyisocyanate>

多異氰酸酯的異氰脲酸酯體可以單獨使用,亦可以組合使用兩種以上。製造多異氰酸酯的異氰脲酸酯體時,多異氰酸酯可以單獨使用,亦可以組合使用兩種以上。多異氰酸酯可例示上述的多異氰酸酯等。 The isocyanurate body of the polyisocyanate may be used alone, or two or more kinds may be used in combination. When producing an isocyanurate body of polyisocyanate, the polyisocyanate may be used alone or in combination of two or more. The polyisocyanate can be exemplified by the above-mentioned polyisocyanates and the like.

多異氰酸酯的異氰脲酸酯體可例示下述通式所表示的化合物等。 Examples of the isocyanurate body of the polyisocyanate include compounds represented by the following general formula.

Figure 108124543-A0202-12-0028-9
Figure 108124543-A0202-12-0028-9

[式中,ni為0以上的整數,RiA~RiE各自獨立地為亞烷基或亞芳基,R~R各自獨立地為異氰酸酯基或

Figure 108124543-A0202-12-0028-10
[In the formula, n i is an integer of 0 or more, R iA to R iE are each independently an alkylene group or an arylene group, and R to R are each independently an isocyanate group or
Figure 108124543-A0202-12-0028-10

(ni1為0以上的整數,Ri1~Ri5各自獨立地為亞烷基或亞芳基,Ri’~Ri”各自獨立地為異氰酸酯基或R~R本身的基團。 (n i1 is an integer of 0 or more, R i1 to R i5 are each independently an alkylene group or an arylene group, and R i ′ to R i ”are each independently an isocyanate group or a group of R to R itself.

Ri4~Ri5、Ri”在各個構成單元中基團可以不同。)。 R i4 ~R i5 and R i ”may be different in each constituent unit.).

RiD~RiE、R在各個構成單元中基團可以不同。] R iD ~R iE and R may be different in each constituent unit. ]

多異氰酸酯的異氰脲酸酯體,可例示Duranate TPA-100、Duranate TKA-100、Duranate MFA-75B、Duranate MHG-80B(以上為旭化成股份有限公司製造)、Coronate HXR(六亞甲基二異氰酸酯的異氰脲酸酯體)(以上為東曹股份有限公司製造)、Takenate D-127N(氫化苯二亞甲基二異氰酸酯的異氰脲酸酯體)(以上為三井化學股份有限公司製造)、VESTANAT T1890/100(異佛爾酮二異氰酸酯的異氰脲酸酯體(以上為贏創日本股份有限公司製造)等。 Isocyanurate body of polyisocyanate, such as Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, Duranate MHG-80B (above manufactured by Asahi Kasei Corporation), Coronate HXR (hexamethylene diisocyanate (Isocyanurate body) (the above is manufactured by Tosoh Corporation), Takenate D-127N (isocyanurate body of hydrogenated xylylene diisocyanate) (the above is manufactured by Mitsui Chemicals Co., Ltd.) , VESTANAT T1890/100 (isocyanurate body of isophorone diisocyanate (above manufactured by Evonik Japan Co., Ltd.), etc.

在一個實施型態中,多異氰酸酯的異氰脲酸酯體的重均分子量(Mw)理想為500~1500。 In one embodiment, the isocyanurate body of the polyisocyanate preferably has a weight average molecular weight (Mw) of 500 to 1500.

在一個實施型態中,多異氰酸酯的異氰脲酸酯體的數均分子量(Mn)理想為500~1500。 In one embodiment, the number average molecular weight (Mn) of the isocyanurate body of the polyisocyanate is preferably 500-1500.

在一個實施型態中,多異氰酸酯的異氰脲酸酯體的分子量分布(Mw/Mn)理想為1.0~1.5。 In one embodiment, the molecular weight distribution (Mw/Mn) of the isocyanurate body of the polyisocyanate is preferably 1.0 to 1.5.

在一個實施型態中,多異氰酸酯的異氰脲酸酯體的NCO含有率(NCO%)理想為5~30質量%。 In one embodiment, the NCO content (NCO%) of the isocyanurate body of the polyisocyanate is desirably 5 to 30% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的多異氰酸酯的異氰脲酸酯體的含量,理想為1~99質量%。 In one embodiment, the content of the isocyanurate body of the polyisocyanate in the self-healing coating agent is preferably 1 to 99% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的選自由含羥基的(甲基)丙烯酸樹脂、及含羥基的聚矽氧烷所成群中的一種以上的總含量與多異氰酸酯的異氰脲酸酯體的質量比(選自由含羥基的(甲基)丙烯酸樹脂、及含羥基的聚矽氧烷所成群中的一種以上的總含量mass/多異氰酸酯的異 氰脲酸酯體mass)理想為1/0.1~1/5。 In one embodiment, the total content of one or more of the self-healing coating agents selected from the group consisting of hydroxyl-containing (meth)acrylic resins and hydroxyl-containing polysiloxanes and polyisocyanates Mass ratio of isocyanurate body (isocyanurate of total content of more than one kind selected from the group consisting of (meth)acrylic resin containing hydroxyl group and polysiloxane containing hydroxyl group mass /polyisocyanate The body mass ) is ideally 1/0.1~1/5.

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的(甲基)丙烯酸樹脂與多異氰酸酯的異氰脲酸酯體的質量比(含羥基的(甲基)丙烯酸樹脂mass/多異氰酸酯的異氰脲酸酯體mass)理想為1/0.1~1/2。 In one embodiment, the mass ratio of the hydroxyl-containing (meth)acrylic resin to the polyisocyanate isocyanurate body (hydroxyl-containing (meth)acrylic resin mass / The isocyanurate mass of polyisocyanate is ideally 1/0.1~1/2.

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的聚矽氧烷與多異氰酸酯的異氰脲酸酯體的質量比(含羥基的聚矽氧烷mass/多異氰酸酯的異氰脲酸酯體mass)理想為0.1/1~0.6/1。 In one embodiment, the mass ratio of the hydroxyl group-containing polysiloxane to the isocyanurate body of the polyisocyanate in the self-healing coating agent (the hydroxyl group-containing polysiloxane mass /polyisocyanate The cyanurate mass ) is ideally 0.1/1 to 0.6/1.

在一個實施型態中,上述自我修復性塗覆劑中的多異氰酸酯的加成物與多異氰酸酯的異氰脲酸酯體的質量比(多異氰酸酯的加成物mass/多異氰酸酯的異氰脲酸酯體mass)理想為1/6~1/0.5。 In one embodiment, the mass ratio of the polyisocyanate adduct to the polyisocyanate isocyanurate body in the above-mentioned self-healing coating agent (polyisocyanate adduct mass /polyisocyanate isocyanurate The acid ester mass ) is ideally 1/6~1/0.5.

在一個實施型態中,上述自我修復性塗覆劑中的多異氰酸酯的加成物、及多異氰酸酯的異氰脲酸酯體的總含量,理想為8~25質量%。 In one embodiment, the total content of the polyisocyanate adduct and the isocyanurate body of the polyisocyanate in the self-healing coating agent is preferably 8-25% by mass.

在一個實施型態中,上述自我修復性塗覆劑中的選自多異氰酸酯的加成物、多異氰酸酯的脲基甲酸酯體、多異氰酸酯的縮二脲體、及多異氰酸酯的異氰脲酸酯體中的兩種以上的總含量,理想為10~60質量%。 In one embodiment, the self-healing coating agent is selected from the group consisting of polyisocyanate adducts, polyisocyanate allophanate bodies, polyisocyanate biuret bodies, and polyisocyanate isocyanurates The total content of two or more types in the ester body is preferably 10 to 60% by mass.

<聚碳酸酯多元醇> <polycarbonate polyol>

在本發明中,「聚碳酸酯多元醇」是具有兩個以上碳酸酯基(-O-(C=O)-O-)且具有兩個以上羥基的化合物。聚碳酸酯多元醇,可例示聚碳酸酯二元醇、聚碳酸酯三元醇、聚碳酸酯四元醇等。聚碳酸酯多元醇可以單獨使用,亦可以組合使用兩種以上。又,在本發明的自我修復性塗覆劑中使用聚碳酸酯多元醇的情況下,與使用聚醚多元醇的情況相比,相容性良好。作為使用本發明的自我修復性塗覆劑的薄膜的硬度、防污性優良的理由,雖然還不清 楚準確的機制,但認為與該相容性的良好有關。 In the present invention, "polycarbonate polyol" is a compound having two or more carbonate groups (-O-(C=O)-O-) and having two or more hydroxyl groups. Examples of polycarbonate polyols include polycarbonate diols, polycarbonate triols, and polycarbonate tetraols. The polycarbonate polyol may be used alone or in combination of two or more. In addition, when the polycarbonate polyol is used in the self-healing coating agent of the present invention, the compatibility is better than when the polyether polyol is used. As the reason why the film using the self-healing coating agent of the present invention is excellent in hardness and antifouling property, although the precise mechanism is not clear, it is considered to be related to the good compatibility.

聚碳酸酯多元醇,藉由光氣法、酯交換反應等現有習知的方法合成。例如,以現有習知的方法使1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、3-甲-1,5-戊二醇、1,8-辛二醇、1,9-壬二醇、2-甲-1,8-辛二醇、1,10-癸二醇等多元醇與碳酸二苯酯、碳酸二甲酯、碳酸二乙酯、碳酸二亞乙酯、光氣等碳酸衍生物反應,藉此得到聚碳酸酯多元醇。 Polycarbonate polyols are synthesized by conventional methods such as phosgene method and transesterification reaction. For example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1, Polyols such as 5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decanediol, and diphenyl carbonate, Carbonic acid derivatives such as dimethyl carbonate, diethyl carbonate, diethylene carbonate, and phosgene are reacted to obtain polycarbonate polyols.

聚碳酸酯二元醇的市售品,可例示BENEBiOL(三菱化學股份有限公司製造)、NIPPOLLAN 981(東曹股份有限公司製造)、Duranol G3450J(旭化成股份有限公司製造)、Duranol G3452(旭化成股份有限公司製造)、Duranol T5652(旭化成股份有限公司製造)、KURARAY POLYOL C-590(可樂麗股份有限公司製造)、KURARAY POLYOL C-1090(可樂麗股份有限公司製造)等。 Examples of commercially available polycarbonate diols include BENEBiOL (manufactured by Mitsubishi Chemical Corporation), NIPPOLLAN 981 (manufactured by Tosoh Corporation), Duranol G3450J (manufactured by Asahi Kasei Corporation), and Duranol G3452 (Asahi Chemical Co., Ltd.) (Made by the company), Duranol T5652 (made by Asahi Kasei Corporation), KURARAY POLYOL C-590 (made by Kuraray Co., Ltd.), KURARAY POLYOL C-1090 (made by Kuraray Co., Ltd.), etc.

聚碳酸酯多元醇,可例示脂肪族聚碳酸酯多元醇、芳香族聚碳酸酯多元醇等。 Examples of polycarbonate polyols include aliphatic polycarbonate polyols and aromatic polycarbonate polyols.

脂肪族聚碳酸酯多元醇,可例示直鏈脂肪族聚碳酸酯多元醇、支鏈脂肪族聚碳酸酯多元醇、脂環族聚碳酸酯多元醇等。 Examples of the aliphatic polycarbonate polyol include linear aliphatic polycarbonate polyol, branched aliphatic polycarbonate polyol, and alicyclic polycarbonate polyol.

在一個實施型態中,聚碳酸酯多元醇中,從耐候性及自我修復性的觀點出發,理想為脂肪族聚碳酸酯多元醇,更理想為直鏈脂肪族聚碳酸酯多元醇。 In one embodiment, from the viewpoint of weather resistance and self-healing properties, the polycarbonate polyol is preferably an aliphatic polycarbonate polyol, and more preferably a linear aliphatic polycarbonate polyol.

在一個實施型態中,上述自我修復性塗覆劑中的聚碳酸酯多元醇的含量,理想為10~40質量%。 In one embodiment, the content of the polycarbonate polyol in the self-healing coating agent is ideally 10-40% by mass.

在一個實施型態中,聚碳酸酯多元醇的羥值理想為 100~250mgKOH/g,更理想為100~170mgKOH/g。藉由使聚碳酸酯多元醇的羥值處於上述範圍內,加工性變得更良好。 In one embodiment, the polycarbonate polyol preferably has a hydroxyl value of 100 to 250 mgKOH/g, more preferably 100 to 170 mgKOH/g. By setting the hydroxyl value of the polycarbonate polyol within the above range, the processability becomes better.

在一個實施型態中,聚碳酸酯多元醇的重均分子量(Mw)理想為500~1000,更理想為800~1000。藉由使聚碳酸酯多元醇的重均分子量處於上述範圍內,加工性變得更良好。 In one embodiment, the weight average molecular weight (Mw) of the polycarbonate polyol is preferably 500-1000, more preferably 800-1000. By making the weight average molecular weight of the polycarbonate polyol within the above range, the processability becomes better.

在一個實施型態中,聚碳酸酯多元醇的數均分子量(Mn)理想為500~1000,更理想為800~1000。藉由使聚碳酸酯多元醇的數均分子量處於上述範圍內,加工性變得更良好。 In one embodiment, the number average molecular weight (Mn) of the polycarbonate polyol is preferably 500-1000, and more preferably 800-1000. When the number average molecular weight of the polycarbonate polyol is within the above range, the processability becomes better.

在一個實施型態中,聚碳酸酯多元醇的分子量分布(Mw/Mn)理想為1.0~1.5。 In one embodiment, the molecular weight distribution (Mw/Mn) of the polycarbonate polyol is ideally 1.0 to 1.5.

在一個實施型態中,上述自我修復性塗覆劑中的選自由含羥基的(甲基)丙烯酸樹脂、含羥基的聚矽氧烷、及多異氰酸酯所成群中的一種以上的總含量與聚碳酸酯多元醇的質量比(選自由含羥基的(甲基)丙烯酸樹脂、含羥基的聚矽氧烷、及多異氰酸酯所成群中的一種以上的總含量mass/聚碳酸酯多元醇mass),理想為0.01~70,更理想為0.05~4。 In one embodiment, the total content of the self-healing coating agent selected from the group consisting of hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, and polyisocyanate and Mass ratio of polycarbonate polyol (a total content of one or more selected from the group consisting of hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, and polyisocyanate mass /polycarbonate polyol mass ), ideally 0.01~70, more ideally 0.05~4.

在一個實施型態中,從含羥基的(甲基)丙烯酸樹脂與聚碳酸酯多元醇的相容性良好、塗膜的透明度優良的觀點出發,上述自我修復性塗覆劑中的含羥基的(甲基)丙烯酸樹脂與聚碳酸酯多元醇的質量比(含羥基的(甲基)丙烯酸樹脂mass/聚碳酸酯多元醇mass),理想為3/1~1/4,進一步理想為3/1~1/1。 In one embodiment, from the viewpoint of good compatibility between the hydroxyl-containing (meth)acrylic resin and polycarbonate polyol, and excellent transparency of the coating film, the hydroxyl-containing The mass ratio of (meth)acrylic resin to polycarbonate polyol (hydroxyl-containing (meth)acrylic resin mass /polycarbonate polyol mass ) is preferably 3/1 to 1/4, further preferably 3/ 1~1/1.

在一個實施型態中,上述自我修復性塗覆劑中的含羥基的聚矽氧烷與聚碳酸酯多元醇的質量比(含羥基的聚矽氧烷mass/聚碳酸酯多元醇 mass)理想為0.05~10。 In one embodiment, the mass ratio of hydroxyl-containing polysiloxane to polycarbonate polyol (hydroxyl-containing polysiloxane mass /polycarbonate polyol mass ) in the above-mentioned self-healing coating agent is ideal It is 0.05~10.

在一個實施型態中,上述自我修復性塗覆劑中的多異氰酸酯與聚碳酸酯多元醇的質量比(多異氰酸酯mass/聚碳酸酯多元醇mass)理想為0.2~2.0。 In one embodiment, the mass ratio of polyisocyanate to polycarbonate polyol in the self-healing coating agent (polyisocyanate mass /polycarbonate polyol mass ) is ideally 0.2 to 2.0.

在一個實施型態中,將上述自我修復性塗覆劑中的含羥基的(甲基)丙烯酸樹脂、含羥基的聚矽氧烷、多異氰酸酯及聚碳酸酯多元醇的總含量設為100質量%時,含羥基的(甲基)丙烯酸樹脂的含量理想為30~70質量%,更理想為40~70質量%,進一步更理想為40~60質量%,特別理想為40~55質量%;含羥基的聚矽氧烷的含量理想為1~10質量%,更理想為1~5質量%,進一步更理想為2~5質量%,特別理想為2~3質量%;多異氰酸酯的含量理想為10~50質量%,更理想為10~45質量%,進一步更理想為10~40質量%,特別理想為15~35質量%;聚碳酸酯多元醇的含量理想為15~40質量%,更理想為15~35質量%,進一步更理想為20~35質量%,特別理想為20~30質量%。 In one embodiment, the total content of the hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, polyisocyanate, and polycarbonate polyol in the above-mentioned self-healing coating agent is set to 100 mass %, the content of hydroxyl-containing (meth)acrylic resin is ideally 30 to 70% by mass, more preferably 40 to 70% by mass, further more preferably 40 to 60% by mass, and particularly preferably 40 to 55% by mass; The content of hydroxyl-containing polysiloxane is ideally 1 to 10% by mass, more preferably 1 to 5% by mass, further more preferably 2 to 5% by mass, and particularly ideally 2 to 3% by mass; the content of polyisocyanate is ideal 10 to 50% by mass, more preferably 10 to 45% by mass, further more preferably 10 to 40% by mass, particularly preferably 15 to 35% by mass; the content of polycarbonate polyol is ideally 15 to 40% by mass, It is more desirably 15 to 35% by mass, further more desirably 20 to 35% by mass, and particularly desirably 20 to 30% by mass.

<硬化催化劑> <hardening catalyst>

在一個實施型態中,上述自我修復性塗覆劑可含有硬化催化劑。硬化催化劑可單獨含有或含有兩種以上。 In one embodiment, the self-healing coating agent may contain a hardening catalyst. The hardening catalyst may be contained alone or in combination of two or more.

硬化催化劑,可例示有機金屬催化劑、有機胺催化劑等。 Examples of hardening catalysts include organic metal catalysts and organic amine catalysts.

有機金屬催化劑,可例示有機典型金屬催化劑、有機過渡金屬催化劑等。 Examples of the organometallic catalyst include organic typical metal catalysts, organic transition metal catalysts, and the like.

有機典型金屬催化劑,可例示有機錫催化劑、有機鉍催化劑等。 Typical organic metal catalysts include organic tin catalysts and organic bismuth catalysts.

有機錫催化劑,可例示二月桂酸二丁基錫、二月桂酸二辛基 錫等。 Examples of organotin catalysts include dibutyltin dilaurate and dioctyltin dilaurate.

有機鉍催化劑,可例示辛酸鉍等。 Examples of organic bismuth catalysts include bismuth octoate.

有機過渡金屬催化劑,可例示有機鈦催化劑、有機鋯催化劑、有機鐵催化劑等。 Examples of organic transition metal catalysts include organic titanium catalysts, organic zirconium catalysts, and organic iron catalysts.

有機鈦催化劑,可例示乙醯乙酸乙酯鈦等。 Examples of organic titanium catalysts include ethyl acetoacetate and titanium.

有機鋯催化劑,可例示四乙醯丙酮鋯等。 The organic zirconium catalyst may be exemplified by zirconium tetraacetone acetone.

有機鐵催化劑,可例示乙醯丙酮鐵等。 Examples of organic iron catalysts include acetoacetone iron and the like.

有機胺催化劑,可例示二氮雜雙環辛烷、二甲基環己胺、四甲基丙二胺、乙基嗎福林、二甲基乙醇胺、三乙胺及三亞乙二胺等。 Examples of organic amine catalysts include diazabicyclooctane, dimethylcyclohexylamine, tetramethylpropanediamine, ethylmorpholine, dimethylethanolamine, triethylamine, and triethylenediamine.

在上述自我修復性塗覆劑中含有硬化催化劑的情況下,上述自我修復性塗覆劑中的硬化催化劑的含量的上限可例示1質量%、0.9質量%、0.75質量%、0.5質量%、0.25質量%、0.1質量%、0.09質量%、0.05質量%、0.02質量%等,下限可例示0.9質量%、0.75質量%、0.5質量%、0.25質量%、0.1質量%、0.09質量%、0.05質量%、0.02質量%、0.01質量%等。在一個實施型態中,在上述自我修復性塗覆劑中含有硬化催化劑的情況下,上述自我修復性塗覆劑中的硬化催化劑的含量,理想為約0.01質量%~1質量%。 When the self-healing coating agent contains a hardening catalyst, the upper limit of the content of the hardening catalyst in the self-healing coating agent can be exemplified by 1% by mass, 0.9% by mass, 0.75% by mass, 0.5% by mass, and 0.25 Mass%, 0.1 mass%, 0.09 mass%, 0.05 mass%, 0.02 mass%, etc., the lower limit can be exemplified by 0.9 mass%, 0.75 mass%, 0.5 mass%, 0.25 mass%, 0.1 mass%, 0.09 mass%, 0.05 mass% , 0.02% by mass, 0.01% by mass, etc. In one embodiment, when the self-healing coating agent contains a hardening catalyst, the content of the hardening catalyst in the self-healing coating agent is preferably about 0.01% by mass to 1% by mass.

在一個實施型態中,硬化催化劑中,從硬化性及貯存期、作業性、塗膜外觀的觀點出發,理想為有機錫催化劑,更理想為二月桂酸二辛基錫。 In one embodiment, the curing catalyst is preferably an organotin catalyst from the viewpoint of curability, shelf life, workability, and coating film appearance, and more preferably dioctyltin dilaurate.

<有機溶劑> <organic solvent>

在一個實施型態中,上述自我修復性塗覆劑可含有有機溶劑。有機溶劑可單獨含有或含有兩種以上。有機溶劑可例示:甲乙酮、乙醯丙酮、甲基異 丁基酮及環己酮等酮溶劑;甲苯及二甲苯等芳香族溶劑;甲醇、乙醇、正丙醇、異丙醇及丁醇等醇溶劑;乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、二乙二醇甲乙醚、二乙二醇二乙醚及丙二醇單甲醚乙酸酯等二醇醚溶劑;乙酸乙酯、乙酸丁酯、乙酸甲基賽路蘇及乙酸賽路蘇等酯溶劑;Solvesso #100及Solvesso #150(均為商品名。埃克森公司製造。)等石油類溶劑;氯仿等鹵烷溶劑;二甲基甲醯胺等醯胺溶劑等。其中,從本發明的自我修復性塗覆劑的貯存期的觀點出發,理想為含有酮類有機溶劑,酮類有機溶劑中,理想為含有乙醯丙酮。 In one embodiment, the self-healing coating agent may contain an organic solvent. The organic solvent may be contained alone or in combination of two or more. Examples of organic solvents include ketone solvents such as methyl ethyl ketone, acetone acetone, methyl isobutyl ketone and cyclohexanone; aromatic solvents such as toluene and xylene; alcohols such as methanol, ethanol, n-propanol, isopropanol and butanol Solvents; glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate Solvents; ester solvents such as ethyl acetate, butyl acetate, methyl celulose acetate and celulose acetate; Solvesso #100 and Solvesso #150 (both trade names. manufactured by Exxon Corporation) and other petroleum solvents; Halogen solvents such as chloroform; amide solvents such as dimethylformamide, etc. Among them, from the viewpoint of the pot life of the self-healing coating agent of the present invention, it is preferable to contain a ketone-based organic solvent, and it is preferable to contain acetone in the ketone-based organic solvent.

在上述自我修復性塗覆劑中含有有機溶劑的情況下,上述自我修復性塗覆劑中的有機溶劑的含量的上限可例示90質量%、80質量%、70質量%、60質量%、55質量%等,下限可例示85質量%、80質量%、70質量%、60質量%、55質量%、50質量%、45質量%、40質量%、35質量%、30質量%、25質量%、20質量%等。在一個實施型態中,在上述自我修復性塗覆劑中含有有機溶劑的情況下,上述自我修復性塗覆劑中的有機溶劑的含量理想為約20質量%~90質量%。又,在上述自我修復性塗覆劑中所含的有機溶劑中,可以含有上述含羥基的(甲基)丙烯酸樹脂、上述含羥基的聚矽氧烷、上述多異氰酸酯、上述硬化催化劑中所含的有機溶劑。 In the case where the above-mentioned self-healing coating agent contains an organic solvent, the upper limit of the content of the organic solvent in the above-mentioned self-healing coating agent can be exemplified by 90% by mass, 80% by mass, 70% by mass, 60% by mass, 55 Mass%, etc., the lower limit can be exemplified by 85% by mass, 80% by mass, 70% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass , 20% by mass, etc. In one embodiment, when the self-healing coating agent contains an organic solvent, the content of the organic solvent in the self-healing coating agent is desirably about 20% by mass to 90% by mass. In addition, the organic solvent contained in the self-healing coating agent may contain the hydroxyl group-containing (meth)acrylic resin, the hydroxyl group-containing polysiloxane, the polyisocyanate, and the curing catalyst. Organic solvent.

<添加劑> <additive>

上述自我修復性塗覆劑,可含有除了含羥基的(甲基)丙烯酸樹脂、含羥基的聚矽氧烷、多異氰酸酯、以及聚碳酸酯多元醇、硬化催化劑、有機溶劑以外的試劑作為添加劑。添加劑,可例示阻聚劑、抗氧化劑、光穩定劑、消泡劑、表面調節劑、顏料、抗靜電劑、金屬氧化物微粒分散體、有機微粒分 散體等。在一個實施型態中,作為添加劑的含量的例子,可例示上述自我修復性塗覆劑的約0.1質量%~10質量%、約小於10質量份、約小於5質量份、約小於1質量份、約小於0.1質量份、約小於0.01質量份、約0質量份等。 The self-healing coating agent may contain reagents other than hydroxyl group-containing (meth)acrylic resin, hydroxyl group-containing polysiloxane, polyisocyanate, polycarbonate polyol, hardening catalyst, and organic solvent as additives. Examples of additives include polymerization inhibitors, antioxidants, light stabilizers, defoamers, surface conditioners, pigments, antistatic agents, metal oxide fine particle dispersions, organic fine particle dispersions, and the like. In one embodiment, as an example of the content of the additive, about 0.1% by mass to 10% by mass, about less than 10 parts by mass, about less than 5 parts by mass, and about less than 1 part by mass of the above-mentioned self-healing coating agent may be exemplified. , About less than 0.1 parts by mass, about less than 0.01 parts by mass, about 0 parts by mass, etc.

上述自我修復性塗覆劑,可以藉由包含利用各種習知的手段將含羥基的(甲基)丙烯酸樹脂、含羥基的聚矽氧烷、多異氰酸酯、以及聚碳酸酯多元醇、硬化催化劑、有機溶劑及/或添加劑等混合的步驟的方法等得到。 The above-mentioned self-healing coating agent may include, by various conventional means, a hydroxyl-containing (meth)acrylic resin, a hydroxyl-containing polysiloxane, a polyisocyanate, a polycarbonate polyol, a hardening catalyst, The method of the step of mixing organic solvents and/or additives is obtained.

[硬化物] [Hardened]

本發明提供上述自我修復性塗覆劑的硬化物。製造上述硬化物時的條件,可例示後述的條件等。 The present invention provides a hardened product of the above-mentioned self-healing coating agent. The conditions at the time of manufacturing the above-mentioned cured product may be exemplified below.

[薄膜] [Film]

本發明提供含有上述硬化物的薄膜。 The present invention provides a film containing the above-mentioned cured product.

基材採用各種習知的基材。基材可例示聚碳酸酯薄膜、(甲基)丙烯酸薄膜(聚(甲基)丙烯酸甲酯薄膜等)、聚苯乙烯薄膜、聚酯薄膜、聚烯烴薄膜、環氧樹脂薄膜、三聚氰胺樹脂薄膜、三乙酸纖維素薄膜、ABS薄膜、AS薄膜、降莰烯類樹脂薄膜、環狀烯烴薄膜、聚乙烯醇薄膜等。基材的厚度亦沒有特別限定,理想為約50μm~200μm。此外,塗覆層的厚度並沒有特別限定,理想為約5μm~30μm。 As the substrate, various conventional substrates are used. Examples of the substrate include polycarbonate film, (meth)acrylic film (poly(meth)acrylate film, etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, Cellulose triacetate film, ABS film, AS film, norbornene-based resin film, cyclic olefin film, polyvinyl alcohol film, etc. The thickness of the substrate is also not particularly limited, but it is preferably about 50 μm to 200 μm. In addition, the thickness of the coating layer is not particularly limited, but is preferably about 5 μm to 30 μm.

上述薄膜藉由各種習知的方法製造。在一個實施型態中,薄膜的製造方法包括在基材的至少單面上塗布自我修復性塗覆劑的步驟(塗布步驟)、進行熱硬化而形成自我修復性塗覆劑硬化物層的步驟(熱硬化步驟)。 The above-mentioned film is manufactured by various conventional methods. In one embodiment, the method of manufacturing the film includes a step of applying a self-healing coating agent on at least one side of the substrate (coating step), and a step of thermally curing to form a hardened layer of the self-healing coating agent. (Thermal hardening step).

本發明的薄膜可以在裝飾薄膜的各種層中亦可作為頂塗層 使用。 The film of the present invention can be used as a top coat in various layers of decorative films.

作為裝飾薄膜的種類,可列舉例如按照(1)頂塗層、錨固層、裝飾層、易接著層、塑膠薄膜、功能層、接著層的順序;(2)頂塗層、易接著層、塑膠薄膜、易接著層、裝飾層、功能層、接著層的順序;(3)頂塗層、錨固層、裝飾層、功能層、接著層的順序;(4)頂塗層、錨固層、裝飾層、接著層的順序;(5)頂塗層、裝飾層、接著層的順序 Examples of the types of decorative films include, for example, (1) top coat layer, anchor layer, decorative layer, easy adhesion layer, plastic film, functional layer, and adhesion layer; (2) top coat layer, easy adhesion layer, plastic The order of film, easy adhesion layer, decorative layer, functional layer, and adhesion layer; (3) top coating, anchor layer, decoration layer, functional layer, adhesion layer sequence; (4) top coating, anchor layer, decoration layer 、The order of the next layer; (5) The order of the top coat, decorative layer and the next layer

構成的裝飾薄膜等。又,裝飾層可以具有選自金屬層、氣相沉積層、著色層、印刷層、多色印刷層、全像層等中的一種以上。 Composition of decorative films, etc. In addition, the decorative layer may have one or more types selected from a metal layer, a vapor-deposited layer, a colored layer, a printed layer, a multicolor printed layer, and a holographic layer.

裝飾薄膜,可以藉由利用凹版塗布法、輥塗法、噴塗法、逗號塗布法、唇塗法、凹版印刷法、網版印刷法等現有習知的方法在基材薄膜上塗布、積層各種層而得到。上述各種方法中,從生產率的觀點出發,理想為凹版印刷法。又,在基材薄膜上,若有需要亦可以具有離型層。 The decorative film can be coated and laminated on various layers of the base film by conventional methods such as gravure coating method, roll coating method, spray coating method, comma coating method, lip coating method, gravure printing method, screen printing method, etc. And get. Among the various methods described above, the gravure printing method is desirable from the viewpoint of productivity. In addition, the base film may have a release layer if necessary.

裝飾薄膜的頂塗層,可以藉由利用熱處理使本發明的自我修復性塗覆劑硬化而得到。該熱處理,理想為在80℃~160℃的溫度下加熱30秒至30分鐘。從耐劃傷性優良的觀點出發,如此得到的頂塗層的厚度理想為約5μm~30μm。 The top coat of the decorative film can be obtained by hardening the self-healing coating agent of the present invention by heat treatment. This heat treatment is ideally heated at a temperature of 80°C to 160°C for 30 seconds to 30 minutes. From the viewpoint of excellent scratch resistance, the thickness of the top coat layer thus obtained is desirably about 5 μm to 30 μm.

如此得到的裝飾薄膜,能夠形成於例如行動電話、電視等各種電器製品、汽車或摩托車等各種交通工具等的被裝飾物表面。 The decorative film thus obtained can be formed on the surface of the object to be decorated, such as various electrical products such as mobile phones and televisions, various vehicles such as automobiles and motorcycles.

作為使裝飾薄膜附著於被裝飾物的方法,可以為在用於成型 出被裝飾物的模具內使裝飾薄膜附著的一次裝飾(以下亦稱為「模內裝飾」),亦可以為從模具取出被裝飾物後使裝飾薄膜附著的二次裝飾(以下亦稱為「模外裝飾」、「模製後裝飾」、「覆蓋(overlay)成形」)。裝飾,可以藉由連同基材薄膜一起附著於被裝飾物的貼合如此之方法進行,亦可以藉由使裝飾薄膜附著於被裝飾物後將基材薄膜及離型層剝離的轉印如此之方法進行。作為轉印的具體例,可以列舉模內轉印、覆蓋轉印、熱轉印、水轉印、壓敏轉印等。作為貼合的具體例,可以列舉模內貼合、TOM工藝等。 As a method of attaching the decorative film to the object to be decorated, it may be a primary decoration that attaches the decorative film in the mold for molding the object to be decorated (hereinafter also referred to as "in-mold decoration"), or it may be taken out from the mold The secondary decoration to which the decorative film is attached after being decorated (hereinafter also referred to as "out-of-mold decoration", "post-mold decoration", "overlay molding"). Decoration can be carried out by attaching the substrate film to the object to be decorated together, or by attaching the decoration film to the object to be decorated and transferring the substrate film and the release layer Method. Specific examples of the transfer include in-mold transfer, cover transfer, thermal transfer, water transfer, and pressure-sensitive transfer. Specific examples of the bonding include in-mold bonding and TOM process.

(塗布步驟) (Coating step)

塗布方法,可例示刮棒塗布機塗布、繞線棒塗布、邁爾棒(mayer bar)塗布、氣刀塗布、凹版塗布、反向凹版塗布、膠版印刷、柔版印刷、網版印刷法等。 Examples of the coating method include bar coater coating, wire bar coating, mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing methods.

塗布量並沒有特別限定。關於塗布量,乾燥後的質量通常理想為約0.1g/m2~30g/m2,更理想為約1g/m2~20g/m2The coating amount is not particularly limited. Regarding the coating amount, the mass after drying is usually preferably about 0.1 g/m 2 to 30 g/m 2 , and more preferably about 1 g/m 2 to 20 g/m 2 .

(熱硬化步驟) (Thermosetting step)

乾燥方法可例示利用循風乾燥機等進行的乾燥。乾燥條件可例示在80℃~160℃的溫度下加熱30秒至30分鐘的條件等。作為其他硬化方法,已知有光硬化,但從加工性的觀點出發,更理想為熱硬化。 The drying method can be exemplified by drying using a wind dryer or the like. Examples of drying conditions include heating at a temperature of 80°C to 160°C for 30 seconds to 30 minutes. As another curing method, photo-curing is known, but from the viewpoint of workability, thermal curing is more desirable.

製造薄膜時,根據需要在乾燥之後進行老化處理。作為一例,可例示40℃下72小時的老化處理等。 When manufacturing a film, it is subjected to aging treatment after drying as necessary. As an example, an aging treatment at 40°C for 72 hours and the like can be exemplified.

【實施例】【Example】

以下,通過實施例及比較例對本發明具體地進行說明。但是, 提供上述的理想實施型態的說明及以下的實施例之目的僅在於例示,並不在於限定本發明。因此,本發明的範圍並非限定於本說明書中具體記載的實施型態及實施例,而僅由申請專利範圍限定。此外,在各實施例及比較例中,只要沒有特別說明,則份、%等的數值為質量基準。 Hereinafter, the present invention will be specifically described by Examples and Comparative Examples. However, the purpose of providing the description of the above-mentioned ideal embodiment and the following embodiments is only for illustration, not for limiting the present invention. Therefore, the scope of the present invention is not limited to the embodiments and examples specifically described in this specification, but only by the scope of the patent application. In addition, in each of the Examples and Comparative Examples, unless otherwise specified, the numerical values of parts, %, and the like are based on mass.

<(甲基)丙烯酸樹脂的製備> <Preparation of (meth)acrylic resin>

[樹脂A] [Resin A]

在具備攪拌機、溫度計、回流冷凝管、滴液漏斗及氮氣導入管的反應容器中,投入甲基丙烯酸甲酯(以下亦稱為MMA)58份、丙烯酸正丁酯(以下亦稱為BA)32份、丙烯酸2-羥乙酯(以下亦稱為HEA)10份以及乙酸乙酯412.5份,並將反應系設定為77℃。接著,投入2,2’-偶氮雙異丁腈2.3份,在80℃附近保溫5小時。接著,投入2,2’-偶氮雙異丁腈3.0份,使反應系在相同溫度附近進一步保溫4小時。然後,藉由將反應系冷卻至室溫,得到具有表1所記載的物性的樹脂A的溶液(不揮發成分35%)。 In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube, 58 parts of methyl methacrylate (hereinafter also referred to as MMA) and n-butyl acrylate (hereinafter also referred to as BA) 32 were charged Parts, 10 parts of 2-hydroxyethyl acrylate (hereinafter also referred to as HEA) and 412.5 parts of ethyl acetate, and the reaction system was set to 77°C. Next, 2.3 parts of 2,2'-azobisisobutyronitrile was added, and the temperature was kept at 80°C for 5 hours. Next, 3.0 parts of 2,2'-azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for 4 hours. Then, by cooling the reaction system to room temperature, a solution of resin A having the physical properties described in Table 1 (nonvolatile content 35%) was obtained.

[樹脂B、樹脂C] [Resin B, Resin C]

除了將原料變更為表1所記載的原料以外,以與樹脂A的製備相同的方式進行。將所得到的樹脂B及樹脂C的物性示於表1中。此外,樹脂A、樹脂B、樹脂C的酸值均為0mgKOH/g。 Except that the raw material was changed to the raw material described in Table 1, it was performed in the same manner as the preparation of resin A. Table 1 shows the physical properties of the obtained resin B and resin C. In addition, the acid values of resin A, resin B, and resin C are all 0 mgKOH/g.

Figure 108124543-A0202-12-0039-13
Figure 108124543-A0202-12-0039-13

各原料為質量份單位。 Each raw material is a unit of mass.

MMA:甲基丙烯酸甲酯 MMA: methyl methacrylate

BMA:甲基丙烯酸丁酯 BMA: butyl methacrylate

BA:丙烯酸正丁酯 BA: n-butyl acrylate

HEMA:甲基丙烯酸2-羥乙酯 HEMA: 2-hydroxyethyl methacrylate

HEA:丙烯酸2-羥乙酯 HEA: 2-hydroxyethyl acrylate

<自我修復性塗覆劑的製備> <Preparation of self-healing coating agent>

實施例1 Example 1

使用100.0份的樹脂A、50.0份的聚碳酸酯二元醇(旭化成股份有限公司製造,商品名:Duranol G3450J)(固體成分濃度100%)、27.5份的六亞甲基二異氰酸酯的加成物(旭化成股份有限公司製造,商品名:Duranate E402-80B)(固體成分濃度80%)、19.4份的六亞甲基二異氰酸酯的縮二脲體(旭化成股份有限公司製造,商品名:Duranate 24A100)(固體成分濃度100%)、5.1份的丙烯酸聚合物改性含羥基的聚矽氧烷(畢克化學.日本股份有限公司製造,商品名:BYK-SILCLEAN3700)(固體成分濃度25%)、0.13份的二月桂酸二辛基錫(固體成分濃度100%)(以下亦稱為DOTDL)、121.5份的甲乙酮(以下亦稱為MEK)、以及12.6份的乙醯丙酮(以下亦稱為AcAc)。藉由將上述成分充分混合,製備固體成分濃度38%的自我修復性塗覆劑。 100.0 parts of resin A, 50.0 parts of polycarbonate diol (made by Asahi Kasei Co., Ltd., trade name: Duranol G3450J) (solid content concentration 100%), 27.5 parts of hexamethylene diisocyanate adduct (Made by Asahi Kasei Corporation, trade name: Duranate E402-80B) (solid content concentration 80%), 19.4 parts of biuret of hexamethylene diisocyanate (made by Asahi Kasei Corporation, trade name: Duranate 24A100) (Solid content concentration 100%), 5.1 parts of acrylic polymer modified hydroxyl-containing polysiloxane (Bike Chemical. Japan Co., Ltd., trade name: BYK-SILCLEAN3700) (solid content concentration 25%), 0.13 1 part of dioctyltin dilaurate (solid content concentration 100%) (hereinafter also referred to as DOTDL), 121.5 parts of methyl ethyl ketone (hereinafter also referred to as MEK), and 12.6 parts of acetone (hereinafter also referred to as AcAc) . By thoroughly mixing the above ingredients, a self-healing coating agent with a solid content concentration of 38% was prepared.

實施例2~9及比較例1~4 Examples 2 to 9 and Comparative Examples 1 to 4

關於實施例2~9及比較例1~4的自我修復性塗覆劑,除了將成分組成如下述表2所示進行變更以外,以與實施例1相同的方式製造。又,實施例1~9及比較例1~4的自我修復性塗覆劑的固體成分濃度設定為38%。 The self-healing coating agents of Examples 2 to 9 and Comparative Examples 1 to 4 were produced in the same manner as in Example 1 except that the composition of the ingredients was changed as shown in Table 2 below. Moreover, the solid content concentration of the self-healing coating agent of Examples 1-9 and Comparative Examples 1-4 was set to 38%.

【表2】

Figure 108124543-A0202-12-0041-14
【Table 2】
Figure 108124543-A0202-12-0041-14

Duranate E402-80B:旭化成股份有限公司製造,六亞甲基二異氰酸酯的加成物(固體成分濃度80%) Duranate E402-80B: manufactured by Asahi Kasei Co., Ltd., an adduct of hexamethylene diisocyanate (solid content concentration 80%)

Duranate 24A100:旭化成股份有限公司製造,六亞甲基二異氰酸酯的縮二脲體(固體成分濃度100%) Duranate 24A100: manufactured by Asahi Kasei Corporation, a biuret of hexamethylene diisocyanate (solid content concentration 100%)

Duranate TPA100:旭化成股份有限公司製造,六亞甲基二異氰酸酯的異氰脲酸酯體(固體成分濃度100%) Duranate TPA100: manufactured by Asahi Kasei Co., Ltd., isocyanurate body of hexamethylene diisocyanate (solid content concentration 100%)

Coronate 2793:東曹股份有限公司製造,六亞甲基二異氰酸酯的脲基甲酸酯體(固體成分濃度100%) Coronate 2793: Allophanate body of hexamethylene diisocyanate (solid content concentration 100%) manufactured by Tosoh Corporation

Duranol G3450J:旭化成股份有限公司製造,聚碳酸酯二元醇(固體成分濃度100%,數均分子量800,羥值140mgKOH/g) Duranol G3450J: manufactured by Asahi Kasei Co., Ltd., polycarbonate diol (solid content concentration 100%, number average molecular weight 800, hydroxyl value 140 mgKOH/g)

KURARAY POLYOL C-590:可樂麗股份有限公司製造,聚碳酸酯二元醇(固體成分濃度100%,數均分子量500,羥值224mgKOH/g) KURARAY POLYOL C-590: manufactured by Kuraray Co., Ltd., polycarbonate diol (solid content concentration 100%, number average molecular weight 500, hydroxyl value 224mgKOH/g)

KURARAY POLYOL C-1090:可樂麗股份有限公司製造,聚碳酸酯二元醇(固體成分濃度100%,數均分子量1000,羥值112mgKOH/g) KURARAY POLYOL C-1090: manufactured by Kuraray Co., Ltd., polycarbonate diol (solid content concentration 100%, number average molecular weight 1000, hydroxyl value 112mgKOH/g)

<薄膜的製作> <Fabrication of film>

評價例1 Evaluation Example 1

以使乾燥後的塗膜厚度為10μm的方式將實施例1的自我修復性塗覆劑塗布於市售的聚對苯二甲酸乙二酯薄膜(東洋紡股份有限公司製造,商品名:COSMOSHINE A4100,100μm厚)上,藉由在120℃下乾燥60秒鐘,使其熱硬化。 The self-healing coating agent of Example 1 was applied to a commercially available polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name: COMOSHINE A4100, so that the coating film thickness after drying was 10 μm. 100 μm thick), it is heat-cured by drying at 120° C. for 60 seconds.

評價例2~9及比較評價例1~4 Evaluation Examples 2 to 9 and Comparative Evaluation Examples 1 to 4

將實施例2~9及比較例1~3的自我修復性塗覆劑,以與評價例1相同的方 式製作薄膜。又,比較例4的自我修復性塗覆劑無法硬化而沒有形成薄膜。 The self-healing coating agents of Examples 2 to 9 and Comparative Examples 1 to 3 were prepared in the same manner as in Evaluation Example 1. In addition, the self-healing coating agent of Comparative Example 4 could not be hardened without forming a thin film.

<薄膜的修復性> <Restorability of the film>

在25℃下,利用黃銅刷(亞速旺股份有限公司製造)對各薄膜表面往返10次,形成傷痕後,測量直至薄膜的傷痕消失為止的時間,藉此進行評價。評價基準如下所述。 At 25°C, a brass brush (manufactured by Azov Co., Ltd.) was used to reciprocate the surface of each film 10 times to form a flaw, and then the time until the flaw of the film disappeared was measured for evaluation. The evaluation criteria are as follows.

○:在10秒以內恢復。 ○: Recovery within 10 seconds.

△:在11秒~1分鐘以內恢復。 △: Recovery within 11 seconds to 1 minute.

×:修復耗時1分鐘以上。 ×: Repair takes more than 1 minute.

<薄膜的防污性> <Antifouling properties of film>

利用油性墨水(愛速客樂股份有限公司製造,商品名:PERMANENT MAKER)在薄膜表面標記印記後,立即用乾燥的不織布(旭化成股份有限公司製造,商品名:BEMCOT M-3II)擦掉該印記,藉此進行評價。評價基準如下所述。 Imprint the mark on the surface of the film with oil-based ink (manufactured by Axel Co., Ltd., trade name: PERMANENT MAKER), and immediately wipe off the mark with a dry nonwoven fabric (made by Asahi Kasei Co., Ltd., trade name: BEMCOT M-3II) To evaluate. The evaluation criteria are as follows.

○:用不織布擦拭5次,能夠擦掉。 ○: It can be wiped off with 5 times of wiping with a non-woven cloth.

△:用不織布擦拭5次以上,油性墨水的痕跡變淺。 △: Wiping with a non-woven cloth 5 or more times, the traces of the oily ink become lighter.

×:無法擦掉。 ×: Unable to erase.

<薄膜的斷裂伸長率> <Break elongation of film>

按照JIS K 7127:1999(塑膠-拉伸特性的試驗方法-第三部:薄膜及片材的試驗條件)的試驗條件,實施薄膜單獨的斷裂伸長率的測定。作為薄膜單獨的製作方法,藉由用手將評價例1中製作的位於聚對苯二甲酸乙二酯薄膜上的薄膜剝離而得到。將試驗開始前的薄膜的形狀,設定為寬度5mm、厚度10μm、長度25mm,將試驗速度設定為200mm/分鐘。 In accordance with the test conditions of JIS K 7127:1999 (Plastics-Test Methods for Tensile Properties-Part 3: Test Conditions for Films and Sheets), the elongation at break of the film alone was measured. As a method for producing the film alone, it is obtained by peeling off the film on the polyethylene terephthalate film produced in Evaluation Example 1 by hand. The shape of the film before the start of the test was set to a width of 5 mm, a thickness of 10 μm, and a length of 25 mm, and the test speed was set to 200 mm/min.

斷裂伸長率(%)=100×(L-25)/25 Elongation at break (%)=100×(L-25)/25

L:硬化物斷裂時的硬化物長度 L: length of the hardened material when the hardened material is broken

<薄膜的外觀> <Appearance of film>

以下述基準藉由目視對薄膜進行確認。 The film was visually confirmed according to the following criteria.

○:透明性優良、無異物。 ○: Excellent transparency and no foreign matter.

×:存在異物、污濁。 ×: There is foreign matter or dirt.

Figure 108124543-A0202-12-0044-15
Figure 108124543-A0202-12-0044-15

Claims (7)

一種自我修復性塗覆劑,其特徵係含有含羥基的(甲基)丙烯酸樹脂、含羥基的聚矽氧烷、多異氰酸酯及聚碳酸酯多元醇。 A self-healing coating agent characterized by containing hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, polyisocyanate and polycarbonate polyol. 如申請專利範圍第1項所記載之自我修復性塗覆劑,其中,前述多異氰酸酯包含選自多異氰酸酯的加成物、多異氰酸酯的脲基甲酸酯體、多異氰酸酯的縮二脲體及多異氰酸酯的異氰脲酸酯體中的兩種以上。 The self-healing coating agent as described in item 1 of the patent application scope, wherein the polyisocyanate includes an adduct selected from polyisocyanate, an allophanate body of polyisocyanate, a biuret body of polyisocyanate and Two or more of the isocyanurate body of polyisocyanate. 如申請專利範圍第1或2項所記載之自我修復性塗覆劑,其中,前述含羥基的(甲基)丙烯酸樹脂的玻璃轉變溫度為40~100℃。 The self-healing coating agent as described in item 1 or 2 of the patent application scope, wherein the glass transition temperature of the hydroxyl-containing (meth)acrylic resin is 40 to 100°C. 如申請專利範圍第1至3項中任一項所記載之自我修復性塗覆劑,其中,前述聚碳酸酯多元醇的數均分子量為800~1000。 The self-healing coating agent as described in any one of claims 1 to 3, wherein the polycarbonate polyol has a number average molecular weight of 800 to 1,000. 如申請專利範圍第1至4項中任一項所記載之自我修復性塗覆劑,其中,將前述含羥基的(甲基)丙烯酸樹脂、含羥基的聚矽氧烷、多異氰酸酯及聚碳酸酯多元醇的總含量設為100質量%時,含羥基的(甲基)丙烯酸樹脂的含量為30~70質量%,含羥基的聚矽氧烷的含量為1~10質量%,多異氰酸酯的含量為10~50質量%,聚碳酸酯多元醇的含量為15~40質量%。 The self-healing coating agent as described in any one of claims 1 to 4, wherein the aforementioned hydroxyl-containing (meth)acrylic resin, hydroxyl-containing polysiloxane, polyisocyanate and polycarbonate When the total content of the ester polyol is set to 100% by mass, the content of the hydroxyl group-containing (meth)acrylic resin is 30 to 70% by mass, and the content of the hydroxyl group-containing polysiloxane is 1 to 10% by mass. The content is 10-50% by mass, and the content of the polycarbonate polyol is 15-40% by mass. 一種硬化物,其特徵係其為如申請專利範圍第1至5項中任一項所記載之自我修復性塗覆劑的硬化物。 A hardened product characterized in that it is a hardened product of a self-healing coating agent as described in any one of items 1 to 5 of the patent application. 一種薄膜,其特徵係含有如申請專利範圍第6項所記載之硬化物。 A film characterized by containing a hardened product as described in item 6 of the patent application.
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