JP5411639B2 - Urethane cross-linking room temperature curable composition - Google Patents
Urethane cross-linking room temperature curable composition Download PDFInfo
- Publication number
- JP5411639B2 JP5411639B2 JP2009220742A JP2009220742A JP5411639B2 JP 5411639 B2 JP5411639 B2 JP 5411639B2 JP 2009220742 A JP2009220742 A JP 2009220742A JP 2009220742 A JP2009220742 A JP 2009220742A JP 5411639 B2 JP5411639 B2 JP 5411639B2
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- JP
- Japan
- Prior art keywords
- room temperature
- curable composition
- temperature curable
- weight
- calcium carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Description
本発明は、室温硬化性組成物、詳しくは、比重が小さく、かつ、優れたゴム物性を示す、建築用シーリング材として用いるウレタン架橋系室温硬化性組成物に関する。 The present invention relates to a room temperature curable composition, and more particularly, to a urethane cross-linked room temperature curable composition used as a sealing material for construction, having a low specific gravity and excellent rubber properties.
従来、建築用シーリング材として、末端にイソシアネート基を含むウレタンプレポリマーを含有するウレタン架橋系硬化性組成物が多用されている。近年、これらのシーリング材用組成物として、環境負荷を低減する目的で、優れた運搬性を有する、シーリング材用組成物全体の比重が軽量化された組成物が望まれている。 Conventionally, urethane crosslinkable curable compositions containing a urethane prepolymer containing an isocyanate group at a terminal have been frequently used as a building sealing material. In recent years, as a composition for these sealing materials, for the purpose of reducing the environmental load, a composition having excellent transportability and a reduced specific gravity of the entire composition for sealing materials has been desired.
そこで、シーリング材用組成物の低比重化を目的として、シーリング材用組成物中にマイクロバルーンを含有させた硬化性組成物などが提案されている（特許文献１および特許文献２）。
しかしながら、上記組成物は比重の点で未だ満足できるものではなく、さらなる低比重化が求められている。また、上記組成物はマイクロバルーンを含有することでシーリング材組成物の体積当たりの樹脂成分量が減量されるため、硬化後の上記組成物は、ゴム物性の低下、例えば伸び率の低下および高モジュラス化などによって、シーリング材として使用する際に目地の動きに対する追従性といったシーリング材性能が低下していた。
Therefore, for the purpose of reducing the specific gravity of the sealing material composition, a curable composition containing a microballoon in the sealing material composition has been proposed (Patent Documents 1 and 2).
However, the composition is not yet satisfactory in terms of specific gravity, and further reduction in specific gravity is required. In addition, since the composition contains a microballoon, the amount of the resin component per volume of the sealing material composition is reduced, so that the composition after curing has reduced rubber properties, for example, reduced elongation and high Due to the modulus, etc., the performance of the sealing material, such as the ability to follow the movement of joints, has deteriorated when used as a sealing material.
本発明は、硬化後に優れた物性、とりわけ優れた伸び率およびモジュラスを有し、かつ、組成物全体の比重が軽量化された室温硬化性組成物であって、建築用シーリング材に用いるウレタン架橋系室温硬化性組成物を提供することを課題とする。 The present invention is a room temperature curable composition having excellent physical properties after curing, especially excellent elongation and modulus, and having a reduced specific gravity of the entire composition, and is a urethane cross-linking used for a sealing material for construction An object of the present invention is to provide a system room temperature curable composition.
本発明者らは、室温硬化性樹脂、無機微粉末で表面被覆されたマイクロバルーン、炭素数１６以下の脂肪酸を４０重量％以上含有する表面処理剤で処理され、該表面処理剤量が３．５重量％以上であり、およびＢＥＴ比表面積が１２〜２５ｍ２／ｇである表面処理炭酸カルシウムおよび平均粒径が０．０５〜５μｍである表面未処理炭酸カルシウムを含んでなり、組成物全体の比重が１．０５以下であるウレタン架橋系室温硬化性組成物によって上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors are treated with a room temperature curable resin, a microballoon whose surface is coated with inorganic fine powder, and a surface treatment agent containing 40% by weight or more of a fatty acid having 16 or less carbon atoms, and the amount of the surface treatment agent is 3. A surface-treated calcium carbonate having a BET specific surface area of 12 to 25 m 2 / g and a surface-untreated calcium carbonate having an average particle diameter of 0.05 to 5 μm. It has been found that the above problems can be solved by a urethane cross-linking room temperature curable composition having a specific gravity of 1.05 or less, and the present invention has been completed.
すなわち、本発明には、以下の好適な実施態様が含まれる。
［１］（Ａ）室温硬化性樹脂と、
（Ｂ）無機微粉末で表面被覆されたマイクロバルーンと、
（Ｃ）炭素数１６以下の脂肪酸を４０重量％以上含有する表面処理剤で処理され、該表面処理剤量が３．５重量％以上であり、およびＢＥＴ比表面積が１２〜２５ｍ２／ｇである表面処理炭酸カルシウムと、
（Ｄ）平均粒径が０．０５〜５μｍである表面未処理炭酸カルシウムと
を含んでなり、比重が１．０５以下である、建築用シーリング材に用いるウレタン架橋系室温硬化性組成物。
［２］室温硬化性樹脂（Ａ）が末端イソシアネート基含有ウレタンプレポリマーである、上記［１］に記載のウレタン架橋系室温硬化性組成物。
［３］室温硬化性樹脂（Ａ）を基準として１０重量％以上のマイクロバルーン（Ｂ）を含有する、上記［１］または［２］に記載のウレタン架橋系室温硬化性組成物。
［４］マイクロバルーン（Ｂ）は平均粒径が１０〜１００μｍである、上記［１］〜［３］のいずれかに記載のウレタン架橋系室温硬化性組成物。
［５］マイクロバルーン（Ｂ）は無機微粉末で被覆された樹脂バルーンである、上記［１］〜［４］のいずれかに記載のウレタン架橋系室温硬化性組成物。
［６］マイクロバルーン（Ｂ）は被覆材脱落率が３５重量％以下である、上記［１］〜［５］のいずれかに記載のウレタン架橋系室温硬化性組成物。
［７］表面処理炭酸カルシウム（Ｃ）において、表面処理剤量は４．５重量％以上である、上記［１］〜［６］のいずれかに記載のウレタン架橋系室温硬化性組成物。
［８］表面処理炭酸カルシウム（Ｃ）において、表面処理剤に含まれる炭素数１６以下の脂肪酸は飽和脂肪酸である、上記［１］〜［７］のいずれかに記載のウレタン架橋系室温硬化性組成物。
That is, the following preferred embodiments are included in the present invention.
[1] (A) a room temperature curable resin;
(B) a microballoon whose surface is coated with an inorganic fine powder;
(C) It is treated with a surface treatment agent containing 40% by weight or more of a fatty acid having 16 or less carbon atoms, the amount of the surface treatment agent is 3.5% by weight or more, and the BET specific surface area is 12 to 25 m 2 / g. Some surface treated calcium carbonate,
(D) A urethane cross-linked room temperature curable composition for use in a building sealing material, comprising a surface untreated calcium carbonate having an average particle size of 0.05 to 5 μm and having a specific gravity of 1.05 or less.
[2] The urethane cross-linking room temperature curable composition according to the above [1], wherein the room temperature curable resin (A) is a terminal isocyanate group-containing urethane prepolymer.
[3] The urethane cross-linked room temperature curable composition according to the above [1] or [2], which contains 10% by weight or more of the microballoon (B) based on the room temperature curable resin (A).
[4] The urethane crosslinked room temperature curable composition according to any one of [1] to [3], wherein the microballoon (B) has an average particle size of 10 to 100 μm.
[5] The urethane-crosslinking room temperature curable composition according to any one of [1] to [4], wherein the microballoon (B) is a resin balloon coated with an inorganic fine powder.
[6] The urethane cross-linked room temperature curable composition according to any one of the above [1] to [5], wherein the microballoon (B) has a coating material falling rate of 35% by weight or less.
[7] The urethane cross-linked room temperature curable composition according to any one of the above [1] to [6], wherein in the surface-treated calcium carbonate (C), the amount of the surface treatment agent is 4.5% by weight or more.
[8] In the surface-treated calcium carbonate (C), the fatty acid having 16 or less carbon atoms contained in the surface treatment agent is a saturated fatty acid, and the urethane cross-linking room temperature curability according to any one of the above [1] to [7]. Composition.
本発明のウレタン架橋系室温硬化性組成物は、組成物全体の比重が低く、かつ、建築用シーリング材として優れた伸び率および低モジュラスを有しているので目地の動きに対する追従性が優れている。従って、本発明の室温硬化性組成物は建築用シーリング材として好適に用いることができる。 The urethane cross-linked room temperature curable composition of the present invention has a low specific gravity of the entire composition, and has excellent elongation and low modulus as a sealing material for construction, so it has excellent followability to joint movement. Yes. Therefore, the room temperature curable composition of the present invention can be suitably used as a building sealing material.
本発明のウレタン架橋系室温硬化性組成物は、
（Ａ）室温硬化性樹脂と、
（Ｂ）無機微粉末で被覆されたマイクロバルーンと、
（Ｃ）炭素数１６以下の脂肪酸を４０重量％以上含有する表面処理剤で処理され、該表面処理剤量が３．５重量％以上であり、およびＢＥＴ比表面積が１２〜２５ｍ２／ｇである表面処理炭酸カルシウムと、
（Ｄ）平均粒径が０．０５〜５μｍである表面未処理炭酸カルシウムと
を含んでなる。
The urethane cross-linking room temperature curable composition of the present invention is
(A) a room temperature curable resin;
(B) a microballoon coated with inorganic fine powder;
(C) It is treated with a surface treatment agent containing 40% by weight or more of a fatty acid having 16 or less carbon atoms, the amount of the surface treatment agent is 3.5% by weight or more, and the BET specific surface area is 12 to 25 m 2 / g. Some surface treated calcium carbonate,
(D) It comprises surface untreated calcium carbonate having an average particle size of 0.05 to 5 μm.
本発明のウレタン架橋系室温硬化性組成物（以下、「硬化性組成物」とも称する）には、ポリウレタン系室温硬化性組成物、ポリサルファイド系室温硬化性組成物が含まれる。 The urethane cross-linking room temperature curable composition of the present invention (hereinafter also referred to as “curable composition”) includes a polyurethane room temperature curable composition and a polysulfide room temperature curable composition.
本発明の硬化性組成物は、上記室温硬化性樹脂（Ａ）、上記マイクロバルーン（Ｂ）、上記表面処理炭酸カルシウム（Ｃ）、上記表面未処理炭酸カルシウム（Ｄ）、および必要に応じて、安定剤、充填剤、老化防止剤、接着付与剤、可塑剤、触媒、着色剤、溶剤等の成分を一括して１成分形として用いることができる。
また、本発明の硬化性組成物は、上記室温硬化性樹脂（Ａ）を含んでなる基剤（ポリサルファイド系シーリング材組成物の場合には硬化剤）と硬化剤（ポリサルファイド系シーリング材組成物の場合には基剤）とから構成される２成分形として、使用時に混合し、硬化させて用いることもできる。さらに、着色剤成分や可塑剤等を別構成（トナー）とし、３成分形として用いることも一般的である。
本発明の硬化性組成物は、２成分形とした場合、好適には、上記室温硬化性樹脂（Ａ）および必要に応じて可塑剤、溶剤等を含んでなる基剤（ポリサルファイド系シーリング材組成物の場合には硬化剤）と、硬化成分、上記マイクロバルーン（Ｂ）、上記表面処理炭酸カルシウム（Ｃ）、上記表面未処理炭酸カルシウム（Ｄ）、および必要に応じて、硬化触媒、安定剤、充填剤、老化防止剤、接着付与剤、可塑剤、溶剤等を含んでなる硬化剤（ポリサルファイド系シーリング材組成物の場合には基剤）から構成される。
本発明の硬化性組成物は、３成分形とした場合、好適には、上記室温硬化性樹脂（Ａ）および必要に応じて可塑剤、溶剤等を含んでなる基剤（ポリサルファイド系室温硬化性組成物の場合には硬化剤）と、硬化成分、上記マイクロバルーン（Ｂ）、上記表面処理炭酸カルシウム（Ｃ）、上記表面未処理炭酸カルシウム（Ｄ）、および必要に応じて、硬化触媒、安定剤、充填剤、老化防止剤、接着付与剤、溶剤等を含んでなる硬化剤（ポリサルファイド系室温硬化性組成物の場合には基剤）と、着色剤や可塑剤等を含んでなるトナーから構成される。
本発明の硬化性組成物は、１成分形とした場合、上記硬化成分を含まないが、室温で湿気によって硬化させることができる。
The curable composition of the present invention includes the room temperature curable resin (A), the microballoon (B), the surface treated calcium carbonate (C), the surface untreated calcium carbonate (D), and, if necessary, Components such as a stabilizer, a filler, an anti-aging agent, an adhesion-imparting agent, a plasticizer, a catalyst, a colorant, and a solvent can be collectively used as a one-component form.
Further, the curable composition of the present invention comprises a base comprising the room temperature curable resin (A) (a curing agent in the case of a polysulfide-based sealing material composition) and a curing agent (a polysulfide-based sealing material composition). In some cases, it can be used as a two-component form composed of a base), mixed at the time of use, and cured. Further, it is general to use a three-component form with a colorant component, a plasticizer, and the like as separate components (toner).
When the curable composition of the present invention is in a two-component form, it is preferably a base (polysulfide sealant composition) comprising the room temperature curable resin (A) and, if necessary, a plasticizer, a solvent, and the like. A curing agent in the case of a product), a curing component, the microballoon (B), the surface treated calcium carbonate (C), the surface untreated calcium carbonate (D), and, if necessary, a curing catalyst, a stabilizer. And a curing agent (a base in the case of a polysulfide-based sealing material composition) containing a filler, an anti-aging agent, an adhesion-imparting agent, a plasticizer, a solvent and the like.
When the curable composition of the present invention is in a three-component form, it is preferably a base (polysulfide-based room temperature curable) comprising the room temperature curable resin (A) and, if necessary, a plasticizer, a solvent and the like. In the case of a composition, a curing agent), a curing component, the microballoon (B), the surface-treated calcium carbonate (C), the surface-untreated calcium carbonate (D), and, if necessary, a curing catalyst, stable A toner containing a colorant, a filler, an anti-aging agent, an adhesion-imparting agent, a solvent, etc. (a base in the case of a polysulfide-based room temperature curable composition) and a colorant or a plasticizer. Composed.
When the curable composition of the present invention is in a one-component form, it does not contain the above-mentioned curing component, but can be cured by moisture at room temperature.
本発明の硬化性組成物において、室温硬化性樹脂（Ａ）として、末端イソシアネート基含有ウレタンプレポリマー（以下、末端ＮＣＯ含有プレポリマーと称する）が挙げられる。
当該末端ＮＣＯ含有プレポリマーは、各種のポリオールに対して過剰量のポリイソシアネート化合物を反応（通常、ＯＨ／ＮＣＯ＝１／１．３〜１／３．０）させることによって製造できる。
上記ポリオールとしては、例えば、エチレングリコール、プロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、ショ糖等の多価アルコールにプロピレンオキサイドまたはプロピレンオキサイドとエチレンオキサイド等のアルキレンオキサイドとを付加重合したポリエーテルポリオール類；エチレングリコール、プロピレングリコールおよびこれらのオリゴグリコール類；ブチレングリコール、ヘキシレングリコール、ポリテトラメチレンエーテルグリコール類；ポリカプロラクトンポリオール類；ポリカーボネートポリオール類；ポリエチレンアジペート等のポリエステルポリオール類；ポリブタジエンポリオール類；ヒマシ油等のヒドロキシル基を有する高級脂肪酸エステル類；ポリエーテルポリオール類またはポリエステルポリオール類にビニルモノマーをグラフト化したポリマーポリオール類等が挙げられる。これらは、単独で用いても２種以上を併用してもよい。
In the curable composition of the present invention, examples of the room temperature curable resin (A) include a terminal isocyanate group-containing urethane prepolymer (hereinafter referred to as a terminal NCO-containing prepolymer).
The terminal NCO-containing prepolymer can be produced by reacting an excess amount of a polyisocyanate compound with various polyols (usually OH / NCO = 1 / 1.3 to 1 / 3.0).
Examples of the polyol include, for example, a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, trimethylol propane, pentaerythritol, sorbitol, sucrose, and the like, which is obtained by addition polymerization of propylene oxide or propylene oxide and alkylene oxide such as ethylene oxide. Ether polyols; ethylene glycol, propylene glycol and their oligoglycols; butylene glycol, hexylene glycol, polytetramethylene ether glycols; polycaprolactone polyols; polycarbonate polyols; polyester polyols such as polyethylene adipate; polybutadiene polyols A higher fatty acid ester having a hydroxyl group such as castor oil; Polymer polyols, etc. grafted vinyl monomers Le polyols or polyester polyols and the like. These may be used alone or in combination of two or more.
上記ポリイソシアネート化合物としては、例えば、芳香族、脂肪族または脂環族に属する任意のものを使用し得る。例えば、トリレンジイソシアネート（ＴＤＩ；２，４−異性体、２，６−異性体およびその混合物）、ジフェニルメタンジイソシアネート（ＭＤＩ）、３，３’−ジメチル−４，４’−ビフェニレンジイソシアネート、１，４−フェニレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、ナフチレンジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネート、クルードＴＤＩ、クルードＭＤＩ、ポリメチレン・ボリフェニルイソシアネート、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート、および水素化キシリレンジイソシアネート、ならびにこれらのイソシアヌレート化物、カルボジイミド化物、ビューレット化物等が挙げられる。これらは、単独で用いても２種以上を併用してもよい。 As said polyisocyanate compound, the arbitrary thing which belongs to aromatic, aliphatic, or alicyclic can be used, for example. For example, tolylene diisocyanate (TDI; 2,4-isomer, 2,6-isomer and mixtures thereof), diphenylmethane diisocyanate (MDI), 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 1,4 -Phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, crude TDI, crude MDI, polymethylene polyphenyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and hydrogenation Examples thereof include xylylene diisocyanate, and isocyanurates, carbodiimides, and burettes. These may be used alone or in combination of two or more.
本発明の硬化性組成物において、上記室温硬化性樹脂（Ａ）は、単独で用いても２種以上を併用してもよい。
本発明の硬化性組成物は、硬化性組成物全量に対して、好適には１０重量％以上、より好適には１５重量％以上の室温硬化性樹脂（Ａ）を含有する。また、本発明の硬化性組成物は、硬化性組成物全量に対して、好適には４５重量％以下、より好適には３５重量％以下の室温硬化性樹脂（Ａ）を含有する。本発明の硬化性組成物が上記範囲内で室温硬化性樹脂（Ａ）を含有することは、硬化後物性、接着性、発泡性および施工時の作業性の点から有利である。
In the curable composition of the present invention, the room temperature curable resin (A) may be used alone or in combination of two or more.
The curable composition of the present invention preferably contains 10% by weight or more, more preferably 15% by weight or more of the room temperature curable resin (A) based on the total amount of the curable composition. Further, the curable composition of the present invention contains 45% by weight or less, more preferably 35% by weight or less, of room temperature curable resin (A) with respect to the total amount of the curable composition. When the curable composition of the present invention contains the room temperature curable resin (A) within the above range, it is advantageous from the viewpoint of physical properties after curing, adhesiveness, foamability and workability during construction.
本発明の硬化性組成物は、２成分形または３成分形とした場合、硬化成分としてポリオールを含むことができる。
上記ポリオールとしては、例えば、エチレングリコール、プロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、ショ糖等の多価アルコールにプロピレンオキサイドまたはプロピレンオキサイドとエチレンオキサイド、等のアルキレンオキサイドとを付加重合したポリエーテルポリオール類；エチレングリコール、プロピレングリコールおよびこれらのオリゴグリコール類；ブチレングリコール、ヘキシレングリコール、ポリテトラメチレンエーテルグリコール類；ポリカプロラクトンポリオール類；ポリカーボネートポリオール類；ポリエチレンアジペート等のポリエステルポリオール類；ポリブタジエンポリオール類；ヒマシ油等のヒドロキシル基を有する高級脂肪酸エステル類；ポリエーテルポリオール類またはポリエステルポリオール類にビニルモノマーをグラフト化したポリマーポリオール類等が挙げられる。これらは、単独で用いても２種以上を併用してもよい。
When the curable composition of the present invention is in a two-component or three-component form, it can contain a polyol as a curable component.
Examples of the polyol include addition polymerization of propylene oxide or propylene oxide and alkylene oxide such as ethylene oxide to polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose. Polyether polyols; ethylene glycol, propylene glycol and their oligoglycols; butylene glycol, hexylene glycol, polytetramethylene ether glycols; polycaprolactone polyols; polycarbonate polyols; polyester polyols such as polyethylene adipate; Higher fatty acid esters having a hydroxyl group such as castor oil; Polymer polyols, etc. grafted vinyl monomer ether polyols or polyester polyols and the like. These may be used alone or in combination of two or more.
本発明の硬化性組成物は、２成分形または３成分形とした場合、硬化成分としてポリサルファイドエーテルポリマーを含むことができる。
本発明で硬化成分として用いる上記ポリサルファイドエーテルポリマー（以下、ポリサルファイドポリマーと称する）とは、主鎖中に式：
−（Ｒ１Ｏ）ｎ−
〔式中、Ｒ１は炭素数２〜４のアルキレン基を示し、ｎは６〜２００の整数を示す〕
で表されるポリエーテル部分と、式：
−（Ｃ２Ｈ４ＯＣｍＨ２ｍＯＣ２Ｈ４−Ｓｘ）− （ａ）
−（ＣＨ２ＣＨ（ＯＨ）ＣＨ２−Ｓｘ）− （ｂ）
〔式中、ｍは１〜２の整数を示し、ｘは１〜５の整数を示す〕
で表される構造単位を含有し、かつ、末端に式：
−Ｃ２Ｈ４ＯＣｍＨ２ｍＯＣ２Ｈ４−ＳＨおよび／または−ＣＨ２ＣＨ（ＯＨ）ＣＨ４−ＳＨ
〔式中、ｍは１〜２の整数を示す〕
で表されるチオール含有基を有するものを指称し、通常、数平均分子量６００〜２０００００、好適には８００〜５００００のものを使用すればよい。市販品としては、東レファインケミカル（株）製の「ＬＰ−２８２」（数平均分子量３５００）等が例示される。なお、かかるポリサルファイドポリマーにあって、上記のポリエーテル部と、構造単位（ａ）および（ｂ）は任意の配列をとることができ、またそれらの占める割合は、ポリエーテル部分が２〜９５％（重量％、以下同様）、構造単位（ａ）：−（Ｃ２Ｈ４ＯＣｍＨ２ｍＯＣ２Ｈ４−Ｓｘ）−部分が３〜７０％、および構造単位（ｂ）：−（ＣＨ２ＣＨ（ＯＨ）ＣＨ２−Ｓｘ）−部分が１〜５０％となるのが好ましい。なお、ポリサルファイド結合Ｓｘの含有量は１〜６０％であるのが好ましい。
また、本発明のポリサルファイド系室温硬化性組成物においては、硬化成分として、上記ポリオールまたはポリサルファイドエーテルポリマーをそれぞれ単独で用いても２種以上を併用してもよく、また、上記ポリオールおよびポリサルファイドエーテルポリマーを併用してもよい。
When the curable composition of the present invention is in a two-component or three-component form, it can contain a polysulfide ether polymer as a curing component.
The polysulfide ether polymer (hereinafter referred to as polysulfide polymer) used as a curing component in the present invention is a compound having the formula:
-(R 1 O) n-
[Wherein R 1 represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 6 to 200]
A polyether moiety represented by the formula:
- (C 2 H 4 OC m H 2m OC 2 H 4 -Sx) - (a)
- (CH 2 CH (OH) CH 2 -Sx) - (b)
[Wherein, m represents an integer of 1 to 2 and x represents an integer of 1 to 5]
Containing a structural unit represented by the formula:
-C 2 H 4 OC m H 2m OC 2 H 4 -SH and / or -CH 2 CH (OH) CH 4 -SH
[Wherein m represents an integer of 1 to 2]
Those having a thiol-containing group represented by the formula: Examples of commercially available products include “LP-282” (number average molecular weight 3500) manufactured by Toray Fine Chemical Co., Ltd. In the polysulfide polymer, the polyether part and the structural units (a) and (b) can have an arbitrary arrangement, and the proportion of the polyether part is 2 to 95% in the polyether part. (wt%, hereinafter the same), the structural unit (a) :-( C 2 H 4 OC m H 2m OC 2 H 4 -Sx) - moiety is 3 to 70%, and structural units (b) :-( CH 2 CH (OH) CH 2 -Sx) - moiety is preferably comprised 1-50%. The content of polysulfide bond Sx is preferably 1 to 60%.
In the polysulfide-based room temperature curable composition of the present invention, the polyol or polysulfide ether polymer may be used alone or in combination of two or more as the curing component, and the polyol and polysulfide ether polymer may be used in combination. May be used in combination.
また、本発明の硬化性組成物は２成分形または３成分形とした場合、硬化性組成物全量に対して、好適には５重量％以上、より好適には１５重量％以上の硬化成分を含有する。また、本発明の硬化性組成物は２成分形とした場合、硬化性組成物全量に対して、好適には４０重量％以下、より好適には３０重量％以下の硬化成分を含有する。本発明の硬化性組成物が上記範囲内で硬化成分を含有することは、硬化後物性、接着性および施工時の作業性の点から有利である。 Further, when the curable composition of the present invention is in a two-component or three-component form, it is preferably 5% by weight or more, more preferably 15% by weight or more of the curable component with respect to the total amount of the curable composition. contains. Further, when the curable composition of the present invention is in a two-component form, it preferably contains 40% by weight or less, more preferably 30% by weight or less of the curable component, based on the total amount of the curable composition. The fact that the curable composition of the present invention contains a curing component within the above range is advantageous from the viewpoint of physical properties after curing, adhesiveness and workability during construction.
本発明の硬化性組成物は、さらに、無機微粉末で表面被覆されたマイクロバルーン（Ｂ）を含有する。マイクロバルーン（Ｂ）としては、例えばフェノール樹脂、エポキシ樹脂、尿素樹脂、塩化ビニリデン樹脂、ポリスチレン樹脂、スチレン系共重合体、ポリメタクリレート、ポリビニルアルコール、塩化ビニリデン−アクリロニトリル共重合体、アクリロニトリル−メタクリロニトリル共重合体、アクリロニトリル−メチルメタクリレート共重合体、塩化ビニリデン−アクリロニトリル−ジビニルベンゼン共重合体などのいずれかから形成される樹脂バルーンまたはガラスバルーンのような無機バルーンの表面の一部または全部が無機微粉末で表面被覆されたものを挙げることができる。無機微粉末で表面被覆された樹脂バルーンは好適である。無機微粉末として、炭酸カルシウム、表面処理炭酸カルシウム、酸化チタン、酸化ケイ素、タルク、クレー、カーボンブラックなどの少なくとも１種または２種以上が使用可能である。中でも、炭酸カルシウムで表面被覆された、アクリロニトリル−メタクリロニトリル共重合体、アクリロニトリル−メチルメタクリレート共重合体から形成された樹脂バルーンは特に好適である。マイクロバルーンを無機微粉末で表面被覆することは生産性、硬化後物性の点で有利である。 The curable composition of the present invention further contains a microballoon (B) whose surface is coated with an inorganic fine powder. Examples of the microballoon (B) include phenol resin, epoxy resin, urea resin, vinylidene chloride resin, polystyrene resin, styrene copolymer, polymethacrylate, polyvinyl alcohol, vinylidene chloride-acrylonitrile copolymer, acrylonitrile-methacrylonitrile. Part or all of the surface of an inorganic balloon such as a resin balloon or a glass balloon formed from any one of a copolymer, an acrylonitrile-methyl methacrylate copolymer, a vinylidene chloride-acrylonitrile-divinylbenzene copolymer, etc. There may be mentioned those whose surface is coated with powder. A resin balloon whose surface is coated with an inorganic fine powder is suitable. As the inorganic fine powder, at least one or more of calcium carbonate, surface-treated calcium carbonate, titanium oxide, silicon oxide, talc, clay, carbon black and the like can be used. Among them, a resin balloon formed from an acrylonitrile-methacrylonitrile copolymer or an acrylonitrile-methyl methacrylate copolymer whose surface is coated with calcium carbonate is particularly suitable. Covering the microballoon with an inorganic fine powder is advantageous in terms of productivity and physical properties after curing.
本発明に用いるマイクロバルーン（Ｂ）は、被覆材脱落率が好適には３５％以下、より好適には３０％以下である。また、本発明に用いるマイクロバルーン（Ｂ）は、被覆材脱落率は０％以上、通常１０％以上である。被覆材脱落率が上記範囲にあるとマイクロバルーン配合による硬化後物性低下の抑制の点で有利である。本発明における被覆材脱落率は、例えば以下の手順で求めることができる。 The microballoon (B) used in the present invention has a coating material drop-off rate of preferably 35% or less, more preferably 30% or less. In addition, the microballoon (B) used in the present invention has a covering material drop-off rate of 0% or more, usually 10% or more. When the covering material drop-off rate is in the above range, it is advantageous from the viewpoint of suppressing deterioration in physical properties after curing due to microballoon blending. The covering material drop-off rate in the present invention can be determined, for example, by the following procedure.
分液ロート中に１００ｍｌのメタノールを投入し、その中へ炭酸カルシウムで表面被覆されたマイクロバルーン約０．５ｇを秤量し投入する。次いで、分液ロートを振盪機にセットし、３０秒間振盪した後、２０分間静置させる。次いで、分液ロートから沈殿物を分取した後、該沈殿物を吸引濾過し、１００℃×２０分間乾燥させる。次いで、濾紙（ガラスフィルター）を１００℃×２０分間乾燥させた後、該沈殿物を秤量する。該沈殿物の重量（脱落量）と投入したマイクロバルーンの重量（投入量）に基づいて、被覆材脱落率（脱落量／投入量）を算出することができる。 100 ml of methanol is put into a separatory funnel, and about 0.5 g of a microballoon whose surface is coated with calcium carbonate is weighed into the separatory funnel. Next, the separatory funnel is set on a shaker, shaken for 30 seconds, and allowed to stand for 20 minutes. Next, after separating the precipitate from the separatory funnel, the precipitate is suction filtered and dried at 100 ° C. for 20 minutes. Next, the filter paper (glass filter) is dried at 100 ° C. for 20 minutes, and the precipitate is weighed. Based on the weight of the precipitate (dropout amount) and the weight of the loaded microballoon (input amount), the coating material dropout rate (dropout amount / input amount) can be calculated.
本発明に用いるマイクロバルーン（Ｂ）は、平均粒径が好適には１０μｍ以上、より好適には３０μｍ以上である。また、本発明に用いるマイクロバルーン（Ｂ）は、平均粒径が好適には１００μｍ以下、より好適には７０μｍ以下である。平均粒径が上記範囲内にあると、本発明の硬化性組成物の製造コスト、ならびにマイクロバルーンのコストと耐圧性のバランスおよび外観の点で有利である。
本発明の硬化性組成物は、室温硬化性樹脂（Ａ）を基準として、好適には１０重量％以上、より好適には１２重量％以上のマイクロバルーン（Ｂ）を含有する。また、本発明の硬化性組成物は、好適には１７重量％以下、より好適には、１５重量％以下のマイクロバルーン（Ｂ）を含有する。マイクロバルーン（Ｂ）が１０重量％以上であると、組成物全体の比重を十分に低下させ得る点で有利である。また、マイクロバルーン（Ｂ）が１７重量％以下であると、良好な硬化後物性が得られる点で有利である。
The microballoon (B) used in the present invention has an average particle size of preferably 10 μm or more, more preferably 30 μm or more. The microballoon (B) used in the present invention has an average particle size of preferably 100 μm or less, more preferably 70 μm or less. When the average particle size is in the above range, it is advantageous in terms of the production cost of the curable composition of the present invention, the balance between the cost and pressure resistance of the microballoon, and the appearance.
The curable composition of the present invention preferably contains 10% by weight or more, more preferably 12% by weight or more of the microballoon (B) based on the room temperature curable resin (A). The curable composition of the present invention preferably contains 17% by weight or less, more preferably 15% by weight or less of the microballoon (B). When the microballoon (B) is 10% by weight or more, it is advantageous in that the specific gravity of the entire composition can be sufficiently reduced. Further, if the microballoon (B) is 17% by weight or less, it is advantageous in that good post-curing physical properties can be obtained.
本発明の硬化性組成物は、室温硬化性樹脂（Ａ）およびマイクロバルーン（Ｂ）に加えて、さらに、炭素数１６以下の脂肪酸が４０重量％以上である表面処理剤、好ましくは炭素数１６以下の脂肪酸が５０重量％以上である表面処理剤、より好ましくは、炭素数１４以下の脂肪酸が５０重量％以上である表面処理剤、さらに好ましくは、炭素数１４以下の脂肪酸が５０重量％以上と炭素数１６以上の不飽和脂肪酸が１５％以上である処理剤で処理され、該表面処理剤量が３．５重量％以上であり、およびＢＥＴ比表面積が１２〜２５ｍ２／ｇである表面処理炭酸カルシウム（Ｃ）を含んでなる。 In addition to the room temperature curable resin (A) and the microballoon (B), the curable composition of the present invention further includes a surface treatment agent having a fatty acid having 16 or less carbon atoms of 40% by weight or more, preferably 16 carbon atoms. A surface treatment agent having 50% by weight or more of the following fatty acid, more preferably a surface treatment agent having 50% by weight or more of a fatty acid having 14 or less carbon atoms, and more preferably 50% by weight or more of a fatty acid having 14 or less carbon atoms. And a surface treatment wherein the amount of the surface treatment agent is 3.5% by weight or more, and the BET specific surface area is 12 to 25 m 2 / g. It comprises treated calcium carbonate (C).
炭素数１６以下の脂肪酸としては酪酸、吉草酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、ミリストレイン酸、ペンタデシル酸、パルミチン酸、パルミトイル酸が挙げられ、中でも硬化性組成物の熱劣化後の物性維持の点で飽和脂肪酸が好適である。このような飽和脂肪酸としては、酪酸、吉草酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸が挙げられ、中でもラウリン酸、ミリスチン酸が好適である。
炭素数１６以上の不飽和脂肪酸としてはパルミトイル酸、オレイン酸、リノール酸、リノレイン酸などが挙げられ、これらは処理剤に含まれると作業性の向上などの点で有利である。
表面処理剤量とは、熱重量分析（ＴＧ）計を用いて、有機物量を測定することによって算出される値であり、表面処理炭酸カルシウムにおける有機物の量のことである。上記表面処理剤量は、好適には４．５重量％以上である。また、上記表面処理剤量は、好適には７重量％以下、より好適には５．５重量％以下である。上記表面処理剤量が、上記範囲にあると、十分なチキソ性を得ることができる。
ＢＥＴ比表面積は、従来既知の方法、例えば、吸着ガスとして窒素を使用し、ＢＥＴ比表面積計を用いて測定する方法によって得ることができる。ＢＥＴ比表面積は、好適には１２〜１８ｍ２／ｇである。ＢＥＴ比表面積が１２ｍ２／ｇ未満の場合、十分なチキソ性が得られない。一方、２５ｍ２／ｇを超える場合には、混合不良や混合時に空気を巻き込み易くやすくなる。
Examples of fatty acids having 16 or less carbon atoms include butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, myristic acid, pentadecylic acid, palmitic acid, and palmitoyl acid. Saturated fatty acids are preferred in terms of maintaining physical properties after heat deterioration. Examples of such saturated fatty acids include butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, and palmitic acid. Of these, lauric acid and myristic acid are preferred.
Examples of unsaturated fatty acids having 16 or more carbon atoms include palmitoyl acid, oleic acid, linoleic acid, linolenic acid, and the like, which are advantageous in terms of improving workability when included in the treatment agent.
The amount of the surface treatment agent is a value calculated by measuring the amount of organic matter using a thermogravimetric analysis (TG) meter, and is the amount of organic matter in the surface treated calcium carbonate. The amount of the surface treatment agent is preferably 4.5% by weight or more. Further, the amount of the surface treatment agent is preferably 7% by weight or less, and more preferably 5.5% by weight or less. When the amount of the surface treatment agent is in the above range, sufficient thixotropy can be obtained.
The BET specific surface area can be obtained by a conventionally known method, for example, a method using nitrogen as an adsorption gas and measuring with a BET specific surface area meter. The BET specific surface area is preferably 12 to 18 m 2 / g. When the BET specific surface area is less than 12 m 2 / g, sufficient thixotropy cannot be obtained. On the other hand, when it exceeds 25 m 2 / g, it becomes easy to entrain air during mixing failure or mixing.
本発明の硬化性組成物において、上記表面処理炭酸カルシウム（Ｃ）は、単独で用いても２種以上を併用してもよい。
本発明の硬化性組成物は、硬化性組成物全量に対して、好適には５重量％以上、より好適には１５重量％以上の表面処理炭酸カルシウム（Ｃ）を含有する。また、本発明の硬化性組成物は、硬化性組成物全量に対して、好適には４５重量％以下、より好適には３５重量％以下の表面処理炭酸カルシウム（Ｃ）を含有する。本発明の硬化性組成物が表面処理炭酸カルシウム（Ｃ）を上記範囲で含有することは、チキソ性付与によるスランプ防止、作業性向上や作業可能時間の点から有利である。
In the curable composition of the present invention, the surface-treated calcium carbonate (C) may be used alone or in combination of two or more.
The curable composition of the present invention preferably contains 5% by weight or more, more preferably 15% by weight or more of the surface-treated calcium carbonate (C) with respect to the total amount of the curable composition. The curable composition of the present invention contains 45% by weight or less, more preferably 35% by weight or less of the surface-treated calcium carbonate (C) with respect to the total amount of the curable composition. The fact that the curable composition of the present invention contains the surface-treated calcium carbonate (C) in the above range is advantageous from the viewpoint of preventing slump by imparting thixotropy, improving workability and possible work time.
本発明の硬化性組成物は、室温硬化性樹脂（Ａ）、マイクロバルーン（Ｂ）および表面処理炭酸カルシウム（Ｃ）に加えて、さらに平均粒径が０.０５〜５μｍである表面未処理炭酸カルシウム（Ｄ）を含有する。平均粒径とは、レーザー回折・散乱式粒度分布測定器において測定された重量累積粒度分布の５０％径である。
上記表面未処理炭酸カルシウム（Ｄ）としては、風化貝殻、粗晶質石灰石、大理石などを乾式粉砕法または湿式粉砕法によって物理的に粉砕分級して製造した重質炭酸カルシウムが好適である。
In addition to room temperature curable resin (A), microballoon (B) and surface-treated calcium carbonate (C), the curable composition of the present invention further has a surface untreated carbonic acid having an average particle size of 0.05 to 5 μm. Contains calcium (D). The average particle diameter is a 50% diameter of the weight cumulative particle size distribution measured by a laser diffraction / scattering particle size distribution analyzer.
As the above-mentioned surface untreated calcium carbonate (D), heavy calcium carbonate produced by physically pulverizing and classifying weathered shells, coarse crystalline limestone, marble and the like by a dry pulverization method or a wet pulverization method is preferable.
上記表面未処理炭酸カルシウム（Ｄ）の平均粒径は、より好適には０．５μｍ以上、さらに好適には１．０μｍ以上である。また、上記表面未処理炭酸カルシウム（Ｄ）の平均粒径は、より好適には４．５μｍ以下、さらに好適には４．０μｍ以下である。平均粒径が小さい場合には、炭酸カルシウム粒子間での凝集を防止するため粒子表面の処理が必要となるため望ましくない。一方、平均粒径が大きい場合には、硬化後ゴム物性の低下、チキソ性低下の点から望ましくない。 The average particle diameter of the surface untreated calcium carbonate (D) is more preferably 0.5 μm or more, and even more preferably 1.0 μm or more. The average particle size of the surface untreated calcium carbonate (D) is more preferably 4.5 μm or less, and even more preferably 4.0 μm or less. When the average particle size is small, it is not desirable because the particle surface needs to be treated to prevent aggregation between the calcium carbonate particles. On the other hand, when the average particle size is large, it is not desirable from the viewpoint of deterioration in rubber physical properties and thixotropy after curing.
本発明の硬化性組成物において、上記表面未処理炭酸カルシウム（Ｄ）は、単独で用いても２種以上を併用してもよい。
本発明の硬化性組成物は、硬化性組成物全量に対して、好適には５重量％以上、より好適には１０重量％以上の表面未処理炭酸カルシウム（Ｄ）を含有する。また、本発明の硬化性組成物は、硬化性組成物全量に対して、好適には４０重量％以下、より好適には２５重量％以下の表面未処理炭酸カルシウム（Ｄ）を含有する。本発明の硬化性組成物が表面未処理炭酸カルシウム（Ｄ）を上記範囲で含有することは作業性、硬化後の物性、特に伸び性の点から有利である。
In the curable composition of the present invention, the surface untreated calcium carbonate (D) may be used alone or in combination of two or more.
The curable composition of the present invention preferably contains 5% by weight or more, more preferably 10% by weight or more of surface untreated calcium carbonate (D), based on the total amount of the curable composition. Moreover, the curable composition of this invention contains 40 weight% or less of surface untreated calcium carbonate (D) suitably with respect to curable composition whole quantity, and more preferably 25 weight% or less. The fact that the curable composition of the present invention contains the untreated calcium carbonate (D) in the above range is advantageous from the viewpoint of workability, physical properties after curing, particularly elongation.
本発明の硬化性組成物は、シーリング材や接着剤などとして有用であるが、その用途および必要に応じて、上記成分（Ａ）〜（Ｄ）および存在する場合には硬化成分に加えて、従来既知の硬化触媒、充填剤、老化防止剤、接着付与剤、可塑剤等の添加剤を硬化剤および／または基剤中に含んでいてもよい。 The curable composition of the present invention is useful as a sealing material, an adhesive and the like, but in addition to the above components (A) to (D) and, if present, the curing component, depending on its use and necessity, Conventionally known additives such as curing catalysts, fillers, anti-aging agents, adhesion-imparting agents, and plasticizers may be contained in the curing agent and / or base.
硬化触媒としては、有機錫化合物、例えば、オクチル酸錫、ナフテン酸錫、ステアリン酸錫、ジブチル錫ジオクトエート、ジブチル錫ジラウレート、ジオクチル錫ジバーサテート、ジブチル錫ビストリエトキシシリケート、ジブチル錫ジオレイルマレート、ジブチル錫ジアセテート、１，１，３，３−テトラブチル−１，３−ジラウリルオキシカルボニル−ジスタノキサン、ジブチル錫オキシビスエトキシシリケート、ジブチル錫オキサイド、ジブチル錫オキサイドとフタル酸エステルとの反応物、ジブチル錫オキサイドとマレイン酸ジエステルとの反応物、ジブチル錫ジアセチルアセトナートなどが挙げられる。その他の有機金属化合物としては、ビスマス、バリウム、カルシウム、インジウム、チタン、ジルコニウム、カルシウム、亜鉛、鉄、コバルト、鉛のカルボン酸（例えば、オクチル酸）塩など、例えば、オクチル酸ビスマス、オクチル酸カルシウムなどが挙げられる。これらは、単独で用いても２種以上を併用してもよい。 Curing catalysts include organic tin compounds such as tin octylate, tin naphthenate, tin stearate, dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin diversate, dibutyltin bistriethoxysilicate, dibutyltin dioleylmalate, dibutyltin. Diacetate, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, dibutyltin oxybisethoxysilicate, dibutyltin oxide, reaction product of dibutyltin oxide and phthalate, dibutyltin oxide And a reaction product of maleic acid diester and dibutyltin diacetylacetonate. Other organometallic compounds include bismuth, barium, calcium, indium, titanium, zirconium, calcium, zinc, iron, cobalt, lead carboxylic acid (for example, octylic acid) salts, such as bismuth octylate, calcium octylate, etc. Etc. These may be used alone or in combination of two or more.
さらに、硬化触媒の水に対する安定性を向上させるため、これらの触媒に加えてカルボン酸を併用することが好適である。これにより、貯蔵中や高温湿度下における作業においても触媒活性の失活が防止され、イソシアネートと、ポリオールまたはポリサルファイドエーテルポリマーとの反応が促進されることにより、イソシアネートと水分の反応による硬化物性の低下やバラツキが少なくなり、さらに表面粘着性が著しく改善される。また、初期の増粘が抑えられるので、可使時間が延長できるという効果も挙げられる。
このようなカルボン酸としては、例えば、安息香酸、フタル酸などの芳香族カルボン酸；オクチル酸（２−エチルヘキサン酸）、ステアリン酸、オレイン酸、リノール酸などの脂肪族カルボン酸；アビエチン酸、ネオアビエチン酸、デヒドロアビエチン酸、ピマール酸、イソピマール酸、パラストリン酸などの樹脂酸が挙げられ、それぞれ単独で用いても２種以上を併用してもよい。なかでも、オクチル酸が好ましい。
Furthermore, in order to improve the stability of the curing catalyst with respect to water, it is preferable to use a carboxylic acid in combination with these catalysts. As a result, deactivation of the catalytic activity is prevented even during storage and operation under high temperature and humidity, and the reaction between the isocyanate and the polyol or polysulfide ether polymer is promoted. Reduction and variation are reduced, and surface tackiness is remarkably improved. In addition, since the initial thickening can be suppressed, there is an effect that the pot life can be extended.
Examples of such carboxylic acids include aromatic carboxylic acids such as benzoic acid and phthalic acid; aliphatic carboxylic acids such as octylic acid (2-ethylhexanoic acid), stearic acid, oleic acid, and linoleic acid; abietic acid, Examples thereof include resin acids such as neoabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid, and parastronic acid, and each may be used alone or in combination of two or more. Of these, octylic acid is preferred.
上記（Ｃ）および（Ｄ）以外の充填剤としては、例えば、脂肪酸処理炭酸カルシウム（上記（Ｃ）に該当しないもの）、ヒュームシリカ、沈降性シリカ、カーボンブラック、タルク、マイカ、クレーや、ガラスビーズ、シラスバルーン、ガラスバルーン、シリカバルーン、プラスチックバルーン、有機粉体コーティングプラスチックバルーンなどのバルーン類、プラスチック粒子、ガラス繊維、金属繊維などの無機繊維、ポリエチレン繊維、ポリプロピレン繊維などの有機繊維、ホウ酸アルミニウム、炭化ケイ素、窒化ケイ素、チタン酸カリウム、グラファイト、針状結晶性炭酸カルシウム、ホウ酸マグネシウム、二ホウ化チタン、クリソタイル、ワラストナイト等の針状結晶性フィラー、アルミフレーク、アルミ粉、鉄粉などが挙げられ、それぞれ単独で用いても２種以上を併用してもよい。 Examples of fillers other than the above (C) and (D) include, for example, fatty acid-treated calcium carbonate (not corresponding to the above (C)), fume silica, precipitated silica, carbon black, talc, mica, clay, and glass. Balloons such as beads, glass balloons, glass balloons, silica balloons, plastic balloons, organic powder coated plastic balloons, inorganic fibers such as plastic particles, glass fibers and metal fibers, organic fibers such as polyethylene fibers and polypropylene fibers, boric acid Acicular crystalline fillers such as aluminum, silicon carbide, silicon nitride, potassium titanate, graphite, acicular crystalline calcium carbonate, magnesium borate, titanium diboride, chrysotile, wollastonite, aluminum flakes, aluminum powder, iron Powder, etc. They are used respectively alone or in a combination of two or more kinds.
可塑剤（減粘剤、粘度調整剤）として、公知のパラフィン系、ナフテン系、ポリブテンなどの炭化水素を、引火点、粘度、塗料付着性などに支障のない範囲で使用することができる。また、フタル酸ジエステル類（ジイソノニルフタレート（ＤＩＮＰ）など）、エポキシ化ヘキサヒドロフタル酸ジエステル類、アルキレンジカルボン酸ジエステル類、アルキルベンゼン類なども塗料付着性、粘度などに支障のない範囲で使用することができる。 As the plasticizer (thickening agent, viscosity modifier), known paraffinic, naphthenic, polybutene and other hydrocarbons can be used as long as the flash point, viscosity, paint adhesion, etc. are not affected. In addition, phthalic acid diesters (such as diisononyl phthalate (DINP)), epoxidized hexahydrophthalic acid diesters, alkylene dicarboxylic acid diesters, alkylbenzenes, etc. may be used within a range that does not affect paint adhesion and viscosity. it can.
その他の添加剤として、必要に応じて、着色剤（ベンガラ、酸化チタン、カーボンブラック、他の着色顔料、染料など）、有機溶剤（アセトン、メチルエチルケトン、リグロイン、酢酸エチル、テトラヒドロフラン、ｎ−ヘキサン、ヘプタンなど）、密着剤（アミノシラン、メルカプトシラン、エポキシシランなどのシランカップリング剤、エポキシ化合物など）、紫外線吸収剤・光安定剤（ベンゾトリアゾール類、ヒンダードアミン類など）、酸化防止剤（ヒンダードフェノール類など）、揺変剤（コロイダルシリカ、有機ベントナイト、脂肪酸アマイド、水添ひまし油など）、溶剤（脂環族炭化水素、芳香族炭化水素など）等を適量範囲で使用できる。これらは、基剤および／または硬化剤に必要に応じて含ませることができる。 As other additives, coloring agents (Bengara, titanium oxide, carbon black, other coloring pigments, dyes, etc.), organic solvents (acetone, methyl ethyl ketone, ligroin, ethyl acetate, tetrahydrofuran, n-hexane, heptane, if necessary. ), Adhesion agents (silane coupling agents such as aminosilane, mercaptosilane, and epoxysilane, epoxy compounds, etc.), UV absorbers and light stabilizers (benzotriazoles, hindered amines, etc.), antioxidants (hindered phenols, etc.) Etc.), thixotropic agents (colloidal silica, organic bentonite, fatty acid amide, hydrogenated castor oil, etc.), solvents (alicyclic hydrocarbons, aromatic hydrocarbons, etc.) and the like can be used in an appropriate amount range. These can be included in the base and / or curing agent as required.
本発明の硬化性組成物は、２成分形とした場合、上記基剤と上記硬化剤から構成され、これらの成分を、例えば、室温条件下で混合し硬化させて使用することができる。
本発明の硬化性組成物は、２成分形ポリウレタン系シーリング材とした場合、上記基剤と上記硬化剤を、好適には１：２〜６、より好適には１：３〜５、さらに好適には１：４〜５の範囲から選択される少なくとも１つの重量比で計量混合し、硬化させて使用することができる。また、本発明の硬化性組成物は、２成分形ポリサルファイド系シーリング材とした場合、上記基剤と上記硬化剤を、好適には１００：５〜４０、より好適には１００：１０〜３０、さらに好適には１００：１５〜２５の範囲から選択される少なくとも１つの重量比で計量混合し、硬化させて使用することができる。
When the curable composition of the present invention is in a two-component form, it is composed of the above-mentioned base and the above-mentioned curing agent, and these components can be used, for example, by mixing and curing at room temperature.
When the curable composition of the present invention is a two-component polyurethane sealant, the base and the curing agent are preferably 1: 2-6, more preferably 1: 3-5, and even more preferably. Can be used after being metered and mixed at at least one weight ratio selected from the range of 1: 4 to 5. When the curable composition of the present invention is a two-component polysulfide-based sealing material, the base and the curing agent are preferably 100: 5 to 40, more preferably 100: 10 to 30, More preferably, it can be metered and mixed at at least one weight ratio selected from the range of 100: 15 to 25 and cured.
本発明の硬化性組成物は、組成物全体の比重が１．０５以下、好適には１．０以下である。また、本発明の硬化性組成物は、硬化後の伸び率が３００％以上、５０％引張応力は０．３Ｎ／ｍｍ２以下である。かかる比重および伸び率を有することにより本発明の硬化性組成物は、建築用シーリング材として好適に用いることができる。 In the curable composition of the present invention, the specific gravity of the entire composition is 1.05 or less, preferably 1.0 or less. The curable composition of the present invention has an elongation percentage after curing of 300% or more and a 50% tensile stress of 0.3 N / mm 2 or less. By having such specific gravity and elongation rate, the curable composition of the present invention can be suitably used as a sealing material for buildings.
以下、実施例および比較例を挙げて本発明をより具体的に説明するが、本発明はこれによって何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited at all by this.
〔実施例１〕
基剤
分子量２０００のポリオール（エクセノール２０２０；旭硝子ウレタン株式会社製）１５０重量部にＴＤＩ（２，４−異性体１００重量％）３０重量部を８５℃にて１０時間反応させた後、ＮＣＯ含有率３．０重量％のプレポリマーを得た。該プレポリマーにイソパラフィン系炭化水素（ＦＰ−３８；出光興産株式会社製）３０重量部を混合攪拌し、基剤を得た。
硬化剤
表１に示す重量の各成分を混合攪拌して硬化剤を得た。
上記のように調製した基剤と硬化剤を１：４（重量比）で混合して、硬化性組成物を得た。
[Example 1]
Base After reacting 30 parts by weight of TDI (2,4-isomer 100% by weight) at 85 ° C. for 10 hours with 150 parts by weight of a polyol having a molecular weight of 2000 (Excenol 2020; manufactured by Asahi Glass Urethane Co., Ltd.), the NCO content rate A 3.0% by weight prepolymer was obtained. 30 parts by weight of isoparaffinic hydrocarbon (FP-38; manufactured by Idemitsu Kosan Co., Ltd.) was mixed and stirred into the prepolymer to obtain a base.
Curing Agent Each component having a weight shown in Table 1 was mixed and stirred to obtain a curing agent.
The base prepared as described above and the curing agent were mixed at 1: 4 (weight ratio) to obtain a curable composition.
〔実施例２〕
実施例１の表面未処理炭酸カルシウム１（三共精粉製エスカロン＃２００、平均粒径４．５μｍ）を、表面未処理炭酸カルシウム２（三共精粉製エスカロン＃２３００、平均粒径１．８μｍ）に代えた以外は、実施例１と同様にして硬化性組成物を得た。
[Example 2]
Surface untreated calcium carbonate 1 (Sankyo Seisaku Escalon # 200, average particle size 4.5 μm) of Example 1 and surface untreated Calcium Carbonate 2 (Sankyo Seisaku Escalon # 2300, mean particle size 1.8 μm) A curable composition was obtained in the same manner as in Example 1 except that.
〔実施例３〕
実施例１のバルーン１（三共精粉製ＥＭＣ−４０Ｓ、平均粒径５０μｍ、被覆材脱落率３０％）をバルーン２（松本油脂製６０ＣＡ、平均粒径６０μｍ、被覆材脱落率４０％）に代えた以外は、実施例１と同様にして硬化性組成物を得た。
Example 3
The balloon 1 (Sankyo Seimitsu EMC-40S, average particle size 50 μm, covering material removal rate 30%) was replaced with balloon 2 (Matsumoto Yushi 60 CA, average particle size 60 μm, coating material removal rate 40%). A curable composition was obtained in the same manner as in Example 1 except that.
〔比較例１〕
実施例１の表面処理炭酸カルシウム１（ラウリン酸被覆コロイド炭酸カルシウム）を表面処理炭酸カルシウム２（ステアリン酸被覆コロイド炭酸カルシウム）に代えた以外は、実施例１と同様にして硬化性組成物を得た。
[Comparative Example 1]
A curable composition was obtained in the same manner as in Example 1 except that the surface-treated calcium carbonate 1 (lauric acid-coated colloidal calcium carbonate) in Example 1 was replaced with the surface-treated calcium carbonate 2 (stearic acid-coated colloidal calcium carbonate). It was.
〔比較例２〕
実施例１の表面処理炭酸カルシウム１（ラウリン酸被覆コロイド炭酸カルシウム）を表面処理炭酸カルシウム２（ステアリン酸被覆コロイド炭酸カルシウム）に代え、表面未処理炭酸カルシウム１（三共精粉製エスカロン＃２００、平均粒径４．５μｍ）を表面未処理炭酸カルシウム３（丸尾カルシウム（株）製スーパーＳ、平均粒径９μｍ）に代えた以外は、実施例１と同様にして硬化性組成物を得た。
[Comparative Example 2]
Surface-treated calcium carbonate 1 (lauric acid-coated colloidal calcium carbonate) of Example 1 was replaced with surface-treated calcium carbonate 2 (stearic acid-coated colloidal calcium carbonate), and surface-untreated calcium carbonate 1 (Escalon # 200, Sankyo Seimitsu Co., Ltd., average) A curable composition was obtained in the same manner as in Example 1 except that the surface untreated calcium carbonate 3 (Super S manufactured by Maruo Calcium Co., Ltd., average particle size 9 μm) was replaced with the surface untreated calcium carbonate 3.
〔比較例３〕
実施例１の表面未処理炭酸カルシウム１（三共精粉製エスカロン＃２００、平均粒径４．５μｍ）を表面未処理炭酸カルシウム４（備北粉化工業株式会社製３００Ｍ、平均粒径１５μｍ）に代えた以外は、実施例１と同様にして硬化性組成物を得た。
[Comparative Example 3]
Surface untreated calcium carbonate 1 (Escalon # 200 made by Sankyo Seimitsu, average particle size 4.5 μm) of Example 1 was replaced with surface untreated calcium carbonate 4 (Bihoku Powder Chemical Co., Ltd. 300M, average particle size 15 μm). A curable composition was obtained in the same manner as in Example 1 except that.
（注１）三洋化成工業株式会社製「サンニックスＧＨ−５０００」」: 分子量５０００のトリオール
（注２）日東化成株式会社製「ネオスタンＵ−６６０」」：オクチル酸ビスマスを主成分とする硬化触媒、ビスマス含有量３％
（注３）日本化学産業株式会社製「ニッカオクチックスＣａ５％」：オクチル酸カルシウムを主成分とする硬化触媒、カルシウム含有量５％
（注４）東亞合成株式会社製「アロニックスＳＴ−３００」
（注５）三共精粉製「ＥＭＣ−４０Ｓ」、平均粒径５０μｍ、被覆材脱落率３０％
（注６）松本油脂製「６０ＣＡ」、平均粒径６０μｍ、被覆材脱落率４０％
（注７）ラウリン酸６０％、オレイン酸２０％被覆コロイド炭酸カルシウム、表面処理剤量４．５％、ＢＥＴ比表面積１４．５ｍ２／ｇ
（注８）ステアリン酸６０％被覆コロイド炭酸カルシウム、表面処理剤量４．５％、ＢＥＴ比表面積１４．５ｍ２／ｇ
（注９）重質炭酸カルシウム、三共精粉製「エスカロン＃２００」、平均粒径４．５μｍ
（注１０）重質炭酸カルシウム、三共精粉製「エスカロン＃２３００」、平均粒径１．８μｍ
（注１１）重質炭酸カルシウム、丸尾カルシウム（株）製「スーパーＳ」、平均粒径６．７μｍ
（注１２）重質炭酸カルシウム、備北粉化工業株式会社製「３００Ｍ」、平均粒径１５μｍ
(Note 1) “SANNICS GH-5000” manufactured by Sanyo Chemical Industries, Ltd .: Triol having a molecular weight of 5000 (Note 2) “Neostan U-660” manufactured by Nitto Kasei Co., Ltd .: Curing catalyst based on bismuth octylate , Bismuth content 3%
(Note 3) “Nikka Octix Ca 5%” manufactured by Nippon Kagaku Sangyo Co., Ltd .: Curing catalyst mainly composed of calcium octylate, calcium content 5%
(Note 4) “Aronix ST-300” manufactured by Toagosei Co., Ltd.
(Note 5) "EMC-40S" made by Sankyo Seiko Co., Ltd., average particle size of 50μm, covering material removal rate of 30%
(Note 6) “60CA” made by Matsumoto Yushi, average particle size 60 μm, covering material drop-off rate 40%
(Note 7) Lauric acid 60%, oleic acid 20% coated colloidal calcium carbonate, surface treatment agent amount 4.5%, BET specific surface area 14.5 m 2 / g
(Note 8) 60% stearic acid-coated colloidal calcium carbonate, surface treatment agent amount 4.5%, BET specific surface area 14.5 m 2 / g
(Note 9) Heavy calcium carbonate, “Escalon # 200” made by Sankyo Seimitsu, average particle size 4.5 μm
(Note 10) Heavy calcium carbonate, “Escalon # 2300” made by Sankyo Seimitsu, average particle size 1.8 μm
(Note 11) Heavy calcium carbonate, “Super S” manufactured by Maruo Calcium Co., Ltd., average particle size 6.7 μm
(Note 12) Heavy calcium carbonate, “300M” manufactured by Bihoku Flour Industry Co., Ltd., average particle size of 15 μm
上記のように調製した各硬化性組成物について以下の性能試験を行った。その結果を表２に示す。 The following performance test was performed about each curable composition prepared as mentioned above. The results are shown in Table 2.
［性能試験方法］
１．比重測定
ＪＩＳ Ｋ ６８３３ ５．２．１「比重カップ法」に準拠して測定した。
[Performance test method]
1. Specific gravity measurement Measured according to JIS K 6833 5.2.1 “Specific gravity cup method”.
２．常態評価
ＪＩＳ Ａ １４３９ ５．２０「引張接着性試験」（２００４）に従い、初期養生後（２０℃×７日＋５０℃×７日）、５０％引張応力［Ｎ／ｍｍ２］、最大引張応力［Ｎ／ｍｍ２］および最大荷重時の伸び率［％］を測定し、さらに接着性を評価した。
接着性判定基準：○；破壊状態が凝集破壊または薄層凝集破壊、×；界面破壊
2. Normal Evaluation According to JIS A 1439 5.20 “Tensile Adhesion Test” (2004), after initial curing (20 ° C. × 7 days + 50 ° C. × 7 days), 50% tensile stress [N / mm 2 ], maximum tensile stress [ N / mm 2 ] and elongation rate [%] at the maximum load were measured, and adhesiveness was further evaluated.
Adhesion criteria: ◯: The fracture state is cohesive failure or thin layer cohesive failure, x: interface fracture
３．耐熱性評価
上記初期養生（２０℃×７日＋５０℃×７日）後、８０℃にて１４日間放置した。その後、５０％引張応力［Ｎ／ｍｍ２］、最大引張応力［Ｎ／ｍｍ２］および最大荷重時の伸び率［％］を測定し、さらに接着性を評価した。
接着性判定基準：○；破壊状態が凝集破壊または薄層凝集破壊、×；界面破壊
3. Evaluation of heat resistance After the initial curing (20 ° C. × 7 days + 50 ° C. × 7 days), the plate was left at 80 ° C. for 14 days. Thereafter, 50% tensile stress [N / mm 2 ], maximum tensile stress [N / mm 2 ] and elongation at maximum load [%] were measured, and adhesiveness was further evaluated.
Adhesion criteria: ◯: The fracture state is cohesive failure or thin layer cohesive failure, x: interface fracture
４．耐水性評価
上記初期養生（２０℃×７日＋５０℃×７日）後、５０℃温水中にて１４日間放置した。その後、上記常態接着性と同様に５０％引張応力［Ｎ／ｍｍ２］、最大引張応力［Ｎ／ｍｍ２］および最大荷重時の伸び率［％］を測定し、さらに接着性を評価した。
接着性判定基準：○；破壊状態が凝集破壊または薄層凝集破壊、×；界面破壊
4). Water resistance evaluation After the initial curing (20 ° C. × 7 days + 50 ° C. × 7 days), the plate was left in 50 ° C. warm water for 14 days. Thereafter, the 50% tensile stress [N / mm 2 ], the maximum tensile stress [N / mm 2 ] and the elongation rate [%] at the maximum load were measured in the same manner as in the normal adhesiveness, and the adhesiveness was further evaluated.
Adhesion criteria: ◯: The fracture state is cohesive failure or thin layer cohesive failure, x: interface fracture
５．接着耐久性評価
ＪＩＳ Ｈ ４０００に規定されるＡ５０５２Ｐアルミニウム板（５０×５０×５ｍｍ）にプライマー（商品名：プライマーＢＣ−３：サンスター技研（株）製）を塗布し、シーリング材を打設する。養生（条件：２０℃×７日＋５０℃×７日）後、シーリング材疲労試験機（東洋精機株式会社製）に試験体を装着し、２３℃雰囲気下にて２０００回（５回／分）の伸縮疲労を与える。伸縮率は±２０％とした。
判定基準：○；破壊しない、△；両端から２ｍｍ以内の破壊、×；破壊する
5. Adhesive durability evaluation A primer (trade name: Primer BC-3: manufactured by Sunstar Giken Co., Ltd.) is applied to an A5052P aluminum plate (50 × 50 × 5 mm) specified in JIS H 4000, and a sealing material is placed. . After curing (conditions: 20 ° C. × 7 days + 50 ° C. × 7 days), the test specimen is mounted on a sealing material fatigue tester (manufactured by Toyo Seiki Co., Ltd.) and 2000 times (5 times / minute) in an atmosphere at 23 ° Gives stretch fatigue. The expansion / contraction rate was ± 20%.
Judgment criteria: ○: Not broken, Δ: Broken within 2 mm from both ends, ×: Destroyed
表２の結果から、実施例１乃至３の硬化性組成物は、組成物全体の比重が１．０以下であることがわかる。また、比較例２および３の硬化性組成物の伸び率が常態、耐熱性、耐水性のいずれの評価においても２２０％以下であるのに対し、実施例１乃至３の硬化性組成物はいずれの場合においても伸び率が３００％以上であることがわかるとともに、比較例１における耐熱劣化後の５０％モジュラスは０．３Ｎ／ｍｍ２を超えている。さらに、表２からは、比較例１乃至３の硬化性組成物では接着耐久性が不十分であるのに対し、実施例１乃至３の硬化性組成物は十分な接着耐久性を有していることがわかる。これらのことから、本発明の硬化性組成物は軽量化されるとともに優れた物性を有することが明らかである。 From the results in Table 2, it can be seen that the specific gravity of the curable compositions of Examples 1 to 3 is 1.0 or less. Further, the elongation percentages of the curable compositions of Comparative Examples 2 and 3 were 220% or less in any evaluation of normal state, heat resistance and water resistance, whereas the curable compositions of Examples 1 to 3 were any. In this case, it can be seen that the elongation is 300% or more, and the 50% modulus after heat resistance deterioration in Comparative Example 1 exceeds 0.3 N / mm 2 . Furthermore, from Table 2, the curable compositions of Comparative Examples 1 to 3 have insufficient adhesion durability, whereas the curable compositions of Examples 1 to 3 have sufficient adhesion durability. I understand that. From these facts, it is clear that the curable composition of the present invention is reduced in weight and has excellent physical properties.
Claims (8)
（Ｂ）無機微粉末で表面被覆されたマイクロバルーンと、
（Ｃ）炭素数１６以下の脂肪酸を４０重量％以上含有する表面処理剤で処理され、該表面処理剤量が３．５重量％以上であり、およびＢＥＴ比表面積が１２〜２５ｍ２／ｇである表面処理炭酸カルシウムと、
（Ｄ）平均粒径が０．０５〜５μｍである表面未処理炭酸カルシウムと
を含んでなり、比重が１．０５以下である、建築用シーリング材として用いるウレタン架橋系室温硬化性組成物。 (A) a room temperature curable resin;
(B) a microballoon whose surface is coated with an inorganic fine powder;
(C) It is treated with a surface treatment agent containing 40% by weight or more of a fatty acid having 16 or less carbon atoms, the amount of the surface treatment agent is 3.5% by weight or more, and the BET specific surface area is 12 to 25 m 2 / g. Some surface treated calcium carbonate,
(D) A urethane cross-linking room temperature curable composition used as a sealing material for building, comprising a surface untreated calcium carbonate having an average particle size of 0.05 to 5 μm and having a specific gravity of 1.05 or less.
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| JP2013204020A (en) * | 2012-03-29 | 2013-10-07 | Yokohama Rubber Co Ltd:The | Curable composition |
| JP6340929B2 (en) * | 2013-07-16 | 2018-06-13 | セメダイン株式会社 | Two-component curable polyurethane sealant composition |
| JP6547299B2 (en) * | 2015-01-08 | 2019-07-24 | セメダイン株式会社 | Two-component curing type polyurethane sealant composition |
| JP7292284B2 (en) * | 2017-12-28 | 2023-06-16 | サンスター技研株式会社 | sealant composition |
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| JP3070775B2 (en) * | 1991-04-30 | 2000-07-31 | 三井化学株式会社 | Molding resin composition and molding resin molding |
| JPH07113073A (en) * | 1993-10-18 | 1995-05-02 | Toray Chiokoole Kk | Matte sealing composition |
| JPH08225738A (en) * | 1994-12-20 | 1996-09-03 | Sekisui Chem Co Ltd | Room-temperature-setting composition |
| US6008271A (en) * | 1995-08-01 | 1999-12-28 | Yokohama Rubber Co., Ltd. | Adhesive composition and process for the production thereof |
| JPH1077409A (en) * | 1996-09-03 | 1998-03-24 | Yokohama Rubber Co Ltd:The | Silicone composition |
| JPH10306210A (en) * | 1997-05-08 | 1998-11-17 | Yokohama Rubber Co Ltd:The | Curable composition |
| JP5428139B2 (en) * | 2007-05-17 | 2014-02-26 | 横浜ゴム株式会社 | Two-component curable polyurethane sealant composition |
| JP5359560B2 (en) * | 2009-05-27 | 2013-12-04 | 横浜ゴム株式会社 | Polyurethane sealant for construction and joint structure after sealing |
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