WO2012049953A1 - Curable resin composition - Google Patents

Curable resin composition Download PDF

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WO2012049953A1
WO2012049953A1 PCT/JP2011/071516 JP2011071516W WO2012049953A1 WO 2012049953 A1 WO2012049953 A1 WO 2012049953A1 JP 2011071516 W JP2011071516 W JP 2011071516W WO 2012049953 A1 WO2012049953 A1 WO 2012049953A1
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component
compound
group
resin composition
curable resin
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PCT/JP2011/071516
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French (fr)
Japanese (ja)
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修 原
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株式会社スリーボンド
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Priority claimed from JP2010231201A external-priority patent/JP5673928B2/en
Priority claimed from JP2010269903A external-priority patent/JP5692511B2/en
Application filed by 株式会社スリーボンド filed Critical 株式会社スリーボンド
Publication of WO2012049953A1 publication Critical patent/WO2012049953A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring

Definitions

  • Patent Document 2 a fluorinating agent is used as an alternative to the organotin compound.
  • sodium fluoride and the like are known to have an effect of strengthening tooth quality and an effect of suppressing the generation of acid of causative bacteria of carious teeth, and is generally used.
  • the fluorinating agent has a strong chemical reducing action, and in some cases, hydrogen fluoride may be generated, which may adversely affect the human body.
  • Cited Document 3 discloses a curable composition that is moisture-cured using phenol or benzoic acid having an electron-withdrawing group.
  • the industrially usable range is not clear. From the examples, substantially only the fluorine-substituted product or acetyl group-substituted product was verified, and as a comparative example, only an unsubstituted product was used.
  • Moisture curable compositions vary greatly depending on the compound having hydrolyzable groups, the type of amine, the type and structure of the catalyst, so whether fluorine-substituted products or acetyl-substituted products can be used in all cases. It is not clear.
  • the present inventors have completed the present invention relating to a resin composition comprising a moisture curable resin, a specific fluorine compound, and an amine compound.
  • the component (A) which is a compound containing two or more hydrolyzable silyl groups in the molecule the component (B) which is a compound represented by the chemical formula 1, and the above (A) (C) component which is an amine compound except a component and (B) component.
  • R 1 is a hydrogen atom, a fluorine atom or a chlorine atom, respectively, and at least one of R 1 is a fluorine atom
  • the component (A) which is a compound containing two or more hydrolyzable silyl groups in the molecule the compound (B) component represented by the chemical formula 4, and the component (A) (C) component which is a removed amine compound.
  • the third embodiment of the present invention is the component (A) which is a compound having two or more hydrolyzable silyl groups of the chemical formula 3 in the molecule, the compound represented by the chemical formula 5 or the chemical formula 6, or a mixture thereof (
  • a curable resin composition comprising a component (B) and a component (C) that is a secondary or tertiary amine excluding the component (A).
  • X is an alkoxy group, an aminoxy group, a ketoxime group, an acetoxy group or an amino group, respectively
  • R 3 is a hydrogen atom or a fluorine atom, respectively, and 1 to 4 R 3 are fluorine atoms
  • the component (A) which is a compound containing two or more hydrolyzable silyl groups in the molecule the component (B) which is a compound represented by the chemical formula 1, and the above (A) (C) component which is an amine compound except a component and (B) component.
  • the component (A) that can be used in the present embodiment is a compound having two or more hydrolyzable silyl groups in the molecule, and the intermolecular cross-linking reaction is initiated by moisture.
  • the site added to the main chain of the hydrolyzable silyl group is not particularly limited. Particularly preferred is a compound having hydrolyzable silyl groups of Chemical Formula 2 and / or Chemical Formula 3 at both ends in the molecule from the viewpoint of achieving both moisture curability and elasticity of the cured product.
  • the number of X in the hydrolyzable silyl group may be an average value contained in the component (A).
  • the component (A) is preferably liquid at 25 ° C. from the viewpoint of handling, and the component (A) having the chemical formula 2 and the component (A) having the chemical formula 3 can be mixed and used.
  • the main chain skeleton of the component (A) include a polyether skeleton, an oxyalkylene skeleton, a (meth) acrylic polymer skeleton, a (meth) acrylic copolymer skeleton, and a polyorganosiloxane skeleton.
  • Particularly preferred is the component (A) in which the (meth) acrylic monomer polymer and / or oxyalkylene polymer (which may be a copolymer) generally called modified silicone is the main chain skeleton. .
  • the component (A) having the chemical formula 2 preferably contains a highly basic tertiary amine in order to increase the crosslinking density.
  • component (A) examples include the Kanyl Corporation Silyl Series, Kaneka MS Polymer Series, MA Series, EP Series, SA Series, OR Series, Asahi Glass Co., Ltd. Exester Series, and the like. However, it is not limited to these.
  • the component (B) that can be used in this embodiment is a fluorine compound having the structure of Chemical Formula 1.
  • R 1 represents a hydrogen atom, a fluorine atom or a chlorine atom, respectively, and at least one of R 1 is a fluorine atom (hereinafter, the component (B) is generically referred to as a pyridine derivative).
  • the component (B) is generically referred to as a pyridine derivative.
  • catalytic performance relating to moisture curing is specifically expressed.
  • the addition amount of the component (B) is preferably 0.01 to 5.0 parts by mass, particularly preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the component (A). It is preferable. Within the above range, the moisture curability is sufficiently developed and the storage stability tends to be stable.
  • the component (C) that can be used in the present embodiment is an amine compound other than the components (A) and (B).
  • the essential component (C) differs depending on the structure of one or more hydrolyzable silyl groups in component (A).
  • a divalent crosslink is formed, and therefore it is preferably a tertiary amine having high crosslink formation promoting performance.
  • a trivalent crosslink is formed, and therefore at least a primary or secondary amine having a low crosslink formation promoting performance is included.
  • the tertiary amine compound may be used in a small amount so that the storage stability does not deteriorate.
  • a compound having a primary, secondary, or tertiary amino group, respectively, is used, as well as a primary, secondary, or primary compound in one molecule.
  • a compound in which a tertiary amino group is mixed can also be used.
  • a compound in which a primary, secondary, or tertiary amino group is mixed is shown as an amine compound having the largest amino group.
  • component (C) examples include primary amines such as hexylamine, dodecylamine, stearylamine, and secondary amines such as di-n-butylamine, dioctylamine, dilaurylamine, and piperidine.
  • primary amines such as hexylamine, dodecylamine, stearylamine, and secondary amines such as di-n-butylamine, dioctylamine, dilaurylamine, and piperidine.
  • tertiary amine include, but are not limited to, triethylamine, tributylamine, trihexylamine and the like.
  • the compound having an amino group and a hydrolyzable silyl group is not particularly limited, and examples thereof include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltriisosilane.
  • examples of the tertiary amine as the component (C) include compounds containing a skeleton such as amidine, guanidine, biguanide, imidazole, diazabicyclo, and pyridine.
  • Specific examples of the compound having an amidine skeleton include guanidine, 1,1,3,3-tetramethyl such as acetamidine, aminoacetamidine, 2,2-dimethylpropionamidine and the like.
  • compounds having a biguanide skeleton such as guanidine, 1-butylguanidine, 1-phenylguanidine, 1-o-tolylguanidine, 1,3-diphenylguanidine, N, N′-diphenylguanidine include butylbiguanide, 1
  • compounds having an imidazole skeleton such as -o-tolylbiguanide and 1-phenylbiguanide include imidazole and 2-ethyl-4-methylimidazole.
  • Examples of compounds having an imidazoline skeleton include 2-methylimidazoline, 2- Undecyl imidazoli As compounds having a diazabicyclo skeleton, such as 2-phenylimidazoline and 4,4-dimethyl-2-imidazoline, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,5,7-triaza Bicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1,8-diazabicyclo [5.4.
  • 2-methylimidazoline 2- Undecyl imidazoli
  • diazabicyclo skeleton such as 2-phenylimidazoline and 4,4-dimethyl-2-imidazoline, 1,4-diazabicyclo [2.2.2] octane (DABCO)
  • DABCO 1,4-diazabicyclo [2.2.2] octane
  • DBU diazabicycloundecene
  • DBA-DBU diazabicycloundecene
  • DBN 1,5-diazabicyclo And [4.3.0] -5-nonene
  • DBN diazabicyclononene
  • pyridine 1,3,4,6,7,8-hexahydro-2H-pyrimidopyridine
  • 1,4,5,6-tetrahydro examples thereof include, but are not limited to, pyrimidine and 1,2-dimethyltetrahydropyrimidine.
  • the component (C) is preferably 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the component (A).
  • the addition amount of the component (C) and the component (B) also affects the moisture curability and the storage stability depending on the ratio, so the ratio of the component (B) to the component (C) is 1: 1 to 1:20. Is most preferred.
  • colorants such as pigments and dyes, metal powder, calcium carbonate, talc, silica, amorphous silica, alumina, aluminum hydroxide and the like are within the range not impairing the characteristics of the present invention.
  • An appropriate amount of additives such as a filler, a flame retardant, an organic filler, a plasticizer, an antioxidant, an antifoaming agent, a coupling agent, a leveling agent, and a rheology control agent may be blended.
  • the component (A) which is a compound containing two or more hydrolyzable silyl groups in the molecule the component (B) which is a compound represented by the chemical formula 4, and the above (A) (C) component which is an amine compound except a component, and a curable resin composition.
  • 3rd embodiment of this invention is (A) component which is a compound which has two or more hydrolysable silyl groups of Chemical formula 3 in a molecule
  • a curable resin composition comprising a component (B) and a component (C) which is a secondary or tertiary amine excluding the component (A).
  • X is an alkoxy group, an aminoxy group, a ketoxime group, an acetoxy group or an amino group, respectively
  • R 3 is a hydrogen atom or a fluorine atom, respectively, and 1 to 4 R 3 are fluorine atoms
  • the component (A) that can be used in the second embodiment and the third embodiment of the present invention for example, the component (A) described above can be used, but the main chain skeleton is the same. Since X reacts independently of each other, the chemical formula 2 and chemical formula 3 have different crosslinking densities after curing. This is presumed to be derived from the number of X in Chemical Formula 2 and Chemical Formula 3. Therefore, the tendency for the (A) component which has Chemical formula 3 to harden
  • the component (A) having the chemical formula 2 is preferably used in combination with a highly basic tertiary amine in order to increase the crosslinking density.
  • the addition amount of the component (B) is preferably 0.01 to 5.0 parts by mass, particularly preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the component (A). When it is within the above range, moisture curability is sufficiently expressed and the storage stability tends to be stable.
  • the component (C) that can be used in the present embodiment is an amine compound other than the component (A).
  • the specific selection of the component (C) differs from the specific combination of the component (A) and the component (B).
  • a primary, secondary, or tertiary amine can be used.
  • a secondary or tertiary amine is suitable.
  • the component (A) has a group represented by the chemical formula 3 and the component (B) is the chemical formula 5 or the chemical formula 6 or a mixture of the chemical formula 5 and the chemical formula 6, a secondary or tertiary amine is suitable.
  • component (C) As a specific example of the component (C), for example, the component (C) described above can be used.
  • inorganic fillers such as pigments, dyes and other colorants, metal powder, calcium carbonate, talc, silica, amorphous silica, alumina, aluminum hydroxide, etc.
  • Additives such as additives, flame retardants, organic fillers, plasticizers, antioxidants, antifoaming agents, coupling agents, leveling agents, and rheology control agents may be blended in appropriate amounts.
  • (C) component was measured and knead
  • the obtained curable resin composition was filled in an airtight container and allowed to stand at 23 ° C. for 24 hours.
  • Detailed preparation amounts follow Tables 1 to 3, and all numerical values are expressed in parts by mass.
  • the curable resin composition applied in the confirmation of surface curability was further allowed to stand for 24 hours, and then the deep curable cured state was evaluated.
  • the cured state is evaluated in three stages as follows, and the result is defined as a “deep cured state”.
  • the deep cured state is preferably a “cured” state.
  • Example 26 The composition obtained by adding heavy calcium carbonate as a filler to Example 15 was measured for viscosity, surface curability, tensile shear bond strength 1 and tensile shear bond strength 2. Furthermore, in order to confirm the storage stability, each test item after being left in a 70 ° C. atmosphere for 5 days was measured. The results are shown in Table 6.
  • Viscosity measurement The viscosity after 3 minutes at 25 ° C. was measured using a cone plate type rotational viscometer. The measurement result is “viscosity (Pa ⁇ s)”. Since the viscosity is appropriately set depending on the amount of filler added, there is no particularly preferred range.
  • Example 7 and Comparative Examples 1 and 2 are compared, when the component (B) is not included or when the component (C) is not included, the moisture curability is very slow, and the component (B) and the component (C) )
  • the composition to which both components are added has a particularly fast moisture-curing property and storage stability.
  • Comparative Examples 3 to 5 add a halogen compound in place of the component (B). In Comparative Example 3, the surface curability is lowered, in Comparative Example 4, the properties are deteriorated, and in Comparative Example 5, the surface curability and the deep part curability are lowered.
  • the hydrolyzable silyl group of the component (A) does not depend on the chemical formula 2 or 3, and depends on the type of the component (C). And has good surface curability. Further, the compositions according to Examples 20 to 24 do not change their properties even when left in an atmosphere at 70 ° C., and have storage stability. Further, as a general tendency of the moisture curable composition, when the filler is added, it becomes difficult for the moisture of the outside air to permeate, so that the surface curability and the deep curability tend to decrease. However, in Example 27, the surface curability was slightly lowered, but the surface curability was maintained to the extent that there was no problem in use.

Abstract

[Problem] The purpose of the present invention is to provide a curable resin composition which contains no organic tin compound, has storage stability and is of a moisture-curable type. The present inventors have made intensive studies for achieving the purpose, and the present invention relating to a resin composition comprising a moisture-curable resin, a specific fluorine compound and an amine compound has been accomplished. [Solution] The curable resin composition comprises: a component (A) which is a compound having at least two hydrolysable silyl groups in the molecule; a component (B) which is a compound represented by chemical formula (1); and a component (C) which is an amine compound other than the components (A) and (B). (In the formula, R1's independently represent a hydrogen atom, a fluorine atom or a chlorine atom, wherein at least one of the R1's represents a fluorine atom.)

Description

硬化性樹脂組成物Curable resin composition
　本発明は、湿気硬化性を有する組成物に関する。 The present invention relates to a composition having moisture curability.
　従来、硬化物が弾性を有する湿気硬化型の組成物（以下、弾性接着剤と呼ぶ。）が知られている。その硬化触媒には、ジブチル錫ジラウレート、ジブチル錫ジアセテート等が汎用的に使用されている。近年、法律によりまたは企業による自主規制により、一部の有機錫化合物に関する使用に規制がかかり始めている。そのため、弾性接着剤に非有機錫化合物を使用する出願が増加している。特許文献１は、その流れのなかで初期の段階で出願された発明である。しかしながら、フッ化ホウ素塩の多くは毒物・劇物に該当する化合物であり、一般消費者にも使用される可能性がある弾性接着剤にそれらを使用するのは好ましくない。 Conventionally, a moisture curable composition (hereinafter referred to as an elastic adhesive) in which a cured product has elasticity is known. As the curing catalyst, dibutyltin dilaurate, dibutyltin diacetate, or the like is generally used. In recent years, the use of some organotin compounds has become regulated by law or by voluntary regulation by companies. Therefore, there are an increasing number of applications that use non-organotin compounds for elastic adhesives. Patent Document 1 is an invention filed at an early stage in the flow. However, many boron fluoride salts are compounds corresponding to poisons and deleterious substances, and it is not preferable to use them for elastic adhesives that may be used by general consumers.
　特許文献２では、有機錫化合物の代替としてフッ素化剤を使用している。一般的に、フッ化ナトリウムなどは歯の質を強くする効果や、むし歯の原因菌の酸の発生を抑えるという作用があると知られおり、汎用的に使用されている。しかしながら、フッ素化剤は化学的な還元作用が強く、場合によってはフッ化水素が発生する恐れがあり、人体に対する悪影響の恐れがある。 In Patent Document 2, a fluorinating agent is used as an alternative to the organotin compound. In general, sodium fluoride and the like are known to have an effect of strengthening tooth quality and an effect of suppressing the generation of acid of causative bacteria of carious teeth, and is generally used. However, the fluorinating agent has a strong chemical reducing action, and in some cases, hydrogen fluoride may be generated, which may adversely affect the human body.
　引用文献３では、電子吸引性基を有するフェノールまたは安息香酸を用いた湿気硬化する硬化性組成物が開示されている。しかしながら、電子吸引性基という広い概念であるため、産業上利用可能な範囲が明確ではない。実施例より、実質的にはフッ素置換体またはアセチル基置換体についてのみ検証され、比較例としては無置換体を行うのみである。湿気硬化性組成物は加水分解性基を有する化合物、アミンの種類、触媒の種類・構造によってその硬化性が大きく変化するため、フッ素置換体、アセチル基置換体がすべてのケースで使用できるかは明確になっていない。 Cited Document 3 discloses a curable composition that is moisture-cured using phenol or benzoic acid having an electron-withdrawing group. However, because of the broad concept of electron-withdrawing groups, the industrially usable range is not clear. From the examples, substantially only the fluorine-substituted product or acetyl group-substituted product was verified, and as a comparative example, only an unsubstituted product was used. Moisture curable compositions vary greatly depending on the compound having hydrolyzable groups, the type of amine, the type and structure of the catalyst, so whether fluorine-substituted products or acetyl-substituted products can be used in all cases. It is not clear.
特開２００５－０５４１７４号公報JP 2005-054174 A 特開２００８－２６０９３２号公報JP 2008-260932 A 特開２００７－１３１７９８号公報JP 2007-131798 A
　従来は、有機錫化合物を使用せず、保存安定性が安定した湿気硬化型の硬化性樹脂組成物を提供するのは困難であった。 Conventionally, it has been difficult to provide a moisture-curable curable resin composition that does not use an organic tin compound and has stable storage stability.
　本発明者らは、上記課題を解決するべく鋭意検討した結果、湿気硬化性樹脂、特定のフッ素化合物、アミン化合物からなる樹脂組成物に関する本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention relating to a resin composition comprising a moisture curable resin, a specific fluorine compound, and an amine compound.
　本発明の第一の実施形態は、分子中に加水分解性シリル基を２以上含有する化合物である（Ａ）成分と、化学式１で示される化合物である（Ｂ）成分と、前記（Ａ）成分および（Ｂ）成分を除いたアミン化合物である（Ｃ）成分と、を含む硬化性樹脂組成物である。 In the first embodiment of the present invention, the component (A) which is a compound containing two or more hydrolyzable silyl groups in the molecule, the component (B) which is a compound represented by the chemical formula 1, and the above (A) (C) component which is an amine compound except a component and (B) component.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
（式中、Ｒ１は、それぞれ、水素原子、フッ素原子または塩素原子であり、Ｒ１の少なくとも１つはフッ素原子である）
　本発明の第二の実施形態は、分子中に加水分解性シリル基を２以上含有する化合物である（Ａ）成分と、化学式４で示される化合物（Ｂ）成分と、前記（Ａ）成分を除いたアミン化合物である（Ｃ）成分と、を含む硬化性樹脂組成物である。 (Wherein R 1 is a hydrogen atom, a fluorine atom or a chlorine atom, respectively, and at least one of R 1 is a fluorine atom)
In the second embodiment of the present invention, the component (A) which is a compound containing two or more hydrolyzable silyl groups in the molecule, the compound (B) component represented by the chemical formula 4, and the component (A) (C) component which is a removed amine compound.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　本発明の第三の実施形態は、分子中に化学式３の加水分解性シリル基を２以上有する化合物である（Ａ）成分と、化学式５または化学式６で示される化合物またはそれらの混合物である（Ｂ）成分と、　前記（Ａ）成分を除いた第二級または第三級アミンである（Ｃ）成分と、を含む硬化性樹脂組成物である。 The third embodiment of the present invention is the component (A) which is a compound having two or more hydrolyzable silyl groups of the chemical formula 3 in the molecule, the compound represented by the chemical formula 5 or the chemical formula 6, or a mixture thereof ( A curable resin composition comprising a component (B) and a component (C) that is a secondary or tertiary amine excluding the component (A).
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
（式中、Ｘは、それぞれ、アルコキシ基、アミノキシ基、ケトオキシム基、アセトキシ基またはアミノ基である） (Wherein X is an alkoxy group, an aminoxy group, a ketoxime group, an acetoxy group or an amino group, respectively)
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
（式中、Ｒ３は、それぞれ、水素原子またはフッ素原子であり、１～４つのＲ３はフッ素原子である） (Wherein R 3 is a hydrogen atom or a fluorine atom, respectively, and 1 to 4 R 3 are fluorine atoms)
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　本発明によれば、有機錫化合物を使用せず、保存安定性を安定した湿気硬化型の硬化性樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a moisture-curable curable resin composition having stable storage stability without using an organic tin compound.
　以下、本発明の実施形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　本発明の第一の実施形態は、分子中に加水分解性シリル基を２以上含有する化合物である（Ａ）成分と、化学式１で示される化合物である（Ｂ）成分と、前記（Ａ）成分および（Ｂ）成分を除いたアミン化合物である（Ｃ）成分と、を含む硬化性樹脂組成物である。 In the first embodiment of the present invention, the component (A) which is a compound containing two or more hydrolyzable silyl groups in the molecule, the component (B) which is a compound represented by the chemical formula 1, and the above (A) (C) component which is an amine compound except a component and (B) component.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
（式中、Ｒ１は、それぞれ、水素原子、フッ素原子または塩素原子であり、Ｒ１の少なくとも１つはフッ素原子である）
　本実施形態で使用することができる（Ａ）成分としては、分子中に加水分解性シリル基を２以上有する化合物であり、湿気により分子間の架橋反応が開始する。当該加水分解性シリル基の主鎖に付加している部位は特に限定されるものではない。特に好ましくは、湿気硬化性と硬化物の弾性を両立する観点から、分子中に化学式２および／または化学式３の加水分解性シリル基を両末端に有する化合物である。前記加水分解性シリル基におけるＸの数は、（Ａ）成分中に含有される平均値であっても良い。 (Wherein R 1 is a hydrogen atom, a fluorine atom or a chlorine atom, respectively, and at least one of R 1 is a fluorine atom)
The component (A) that can be used in the present embodiment is a compound having two or more hydrolyzable silyl groups in the molecule, and the intermolecular cross-linking reaction is initiated by moisture. The site added to the main chain of the hydrolyzable silyl group is not particularly limited. Particularly preferred is a compound having hydrolyzable silyl groups of Chemical Formula 2 and / or Chemical Formula 3 at both ends in the molecule from the viewpoint of achieving both moisture curability and elasticity of the cured product. The number of X in the hydrolyzable silyl group may be an average value contained in the component (A).
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　化学式２または化学式３のＸは、アルコキシ基、アミノキシ基、ケトオキシム基、アセトキシ基またはアミノ基のものを使用することができる。また、化学式２のＲ２は置換または非置換の炭素数１～２０の炭化水素基を示す。（以下、化学式２および化学式３を加水分解性シリル基と総称する。）前記Ｘは、特に好ましくは、アルコキシ基であり、具体的にはメトキシ基、エトキシ基、プロポキシ基、ブトキシ基等が挙げられる。 X in Chemical Formula 2 or Chemical Formula 3 may be an alkoxy group, aminoxy group, ketoxime group, acetoxy group or amino group. In addition, R 2 in Chemical Formula 2 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. (Hereinafter, Chemical Formula 2 and Chemical Formula 3 are collectively referred to as a hydrolyzable silyl group.) X is particularly preferably an alkoxy group, and specific examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. It is done.
　前記（Ａ）成分は、取扱いの観点より２５℃において液体であることが好ましく、化学式２を有する（Ａ）成分と化学式３を有する（Ａ）成分を混合して使用することもできる。（Ａ）成分の主鎖骨格としては、ポリエーテル骨格、オキシアルキレン骨格、（メタ）アクリル重合骨格、（メタ）アクリル共重合骨格、ポリオルガノシロキサン骨格などが挙げられる。特に好ましくは、変性シリコーンと一般的に呼ばれている（メタ）アクリルモノマー重合体および／またはオキシアルキレン重合体（共重合体であってもよい）が主鎖骨格である（Ａ）成分が好ましい。 The component (A) is preferably liquid at 25 ° C. from the viewpoint of handling, and the component (A) having the chemical formula 2 and the component (A) having the chemical formula 3 can be mixed and used. Examples of the main chain skeleton of the component (A) include a polyether skeleton, an oxyalkylene skeleton, a (meth) acrylic polymer skeleton, a (meth) acrylic copolymer skeleton, and a polyorganosiloxane skeleton. Particularly preferred is the component (A) in which the (meth) acrylic monomer polymer and / or oxyalkylene polymer (which may be a copolymer) generally called modified silicone is the main chain skeleton. .
　また、前記主鎖骨格は同じでも、前記Ｘはそれぞれ独立して反応するため、化学式２と化学式３では硬化後の架橋密度が異なる。そのため、化学式２を有する（Ａ）成分は、架橋密度を上げるため、塩基性の強い第三級アミンが含まれることが好ましい。 In addition, even though the main chain skeleton is the same, since the Xs react independently, the crosslink density after curing is different between the chemical formula 2 and the chemical formula 3. Therefore, the component (A) having the chemical formula 2 preferably contains a highly basic tertiary amine in order to increase the crosslinking density.
　前記（Ａ）成分の具体例としては、株式会社カネカ製のサイリルシリーズ、カネカＭＳポリマーシリーズ、ＭＡシリーズ、ＥＰシリーズ、ＳＡシリーズ、ＯＲシリーズ、旭硝子株式会社製のエクセスターシリーズ等が挙げられるが、これらに限定されるわけではない。 Specific examples of the component (A) include the Kanyl Corporation Silyl Series, Kaneka MS Polymer Series, MA Series, EP Series, SA Series, OR Series, Asahi Glass Co., Ltd. Exester Series, and the like. However, it is not limited to these.
　本実施形態で使用することができる（Ｂ）成分としては、化学式１の構造を有するフッ素化合物である。Ｒ１は、それぞれ、水素原子、フッ素原子または塩素原子を示し、Ｒ１の少なくとも１つはフッ素原子である（以下、（Ｂ）成分をピリジン誘導体と総称する。）。前記ピリジン誘導体が（Ｃ）成分と共に存在することによって、湿気硬化に関する触媒性能が特異的に発現される。また、樹脂成分の溶解性など、取扱いの観点から２５℃で液体であることが好ましい。 The component (B) that can be used in this embodiment is a fluorine compound having the structure of Chemical Formula 1. R 1 represents a hydrogen atom, a fluorine atom or a chlorine atom, respectively, and at least one of R 1 is a fluorine atom (hereinafter, the component (B) is generically referred to as a pyridine derivative). By the presence of the pyridine derivative together with the component (C), catalytic performance relating to moisture curing is specifically expressed. Moreover, it is preferable that it is a liquid at 25 degreeC from a viewpoint of handling, such as the solubility of a resin component.
　前記（Ｂ）成分の添加量は、（Ａ）成分１００質量部に対して、０．０１～５．０質量部であることが好ましく、特に好ましくは０．０５～２．０質量部であることが好ましい。前記範囲内では湿気硬化性が充分発現し、また、保存安定性が安定する傾向がある。 The addition amount of the component (B) is preferably 0.01 to 5.0 parts by mass, particularly preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the component (A). It is preferable. Within the above range, the moisture curability is sufficiently developed and the storage stability tends to be stable.
　本実施形態で使用することができる（Ｃ）成分としては、（Ａ）成分および（Ｂ）成分以外のアミン化合物である。（Ａ）成分の１以上の加水分解性シリル基の構造により、必須とされる（Ｃ）成分が異なってくる。（Ａ）成分の１以上の加水分解性シリル基が化学式２で示される場合は２価の架橋を形成するため、架橋の形成促進性能が高い第三級アミンであることが好ましい。一方、（Ａ）成分の１以上の加水分解性シリル基が化学式３で示される場合は３価の架橋を形成するため、少なくとも架橋の形成促進性能が低い第一級または第二級アミンを含んでいれば良く、第三級アミン化合物を保存安定性が低下しない程度に少量使用しても良い。 The component (C) that can be used in the present embodiment is an amine compound other than the components (A) and (B). The essential component (C) differs depending on the structure of one or more hydrolyzable silyl groups in component (A). In the case where one or more hydrolyzable silyl groups of the component (A) are represented by the chemical formula 2, a divalent crosslink is formed, and therefore it is preferably a tertiary amine having high crosslink formation promoting performance. On the other hand, when one or more hydrolyzable silyl groups of the component (A) are represented by the chemical formula 3, a trivalent crosslink is formed, and therefore at least a primary or secondary amine having a low crosslink formation promoting performance is included. The tertiary amine compound may be used in a small amount so that the storage stability does not deteriorate.
　前記（Ｃ）成分において、第一級、第二級、または第三級のアミノ基がそれぞれ存在する化合物を使用することはもちろんのこと、一分子中に第一級、第二級、または第三級のアミノ基が混在する化合物を使用することもできる。本発明においては、第一級、第二級、または第三級のアミノ基が混在する化合物は、最も大きい級のアミノ基を有するアミン化合物として示すものとする。 In the component (C), a compound having a primary, secondary, or tertiary amino group, respectively, is used, as well as a primary, secondary, or primary compound in one molecule. A compound in which a tertiary amino group is mixed can also be used. In the present invention, a compound in which a primary, secondary, or tertiary amino group is mixed is shown as an amine compound having the largest amino group.
　前記（Ｃ）成分の具体例としては、第一級アミンとして、ヘキシルアミン、ドデシルアミン、ステアリルアミン等が、第二級アミンとして、ジｎ－ブチルアミン、ジオクチルアミン、ジラウリルアミン、ピペリジン等が、第三級アミンとして、トリエチルアミン、トリブチルアミン、トリヘキシルアミン等が挙げられるがこれらに限定されるものではない。また、アミノ基と加水分解性シリル基を有する化合物（通称、アミノシラン）としては、特に限定されず、たとえば、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－アミノプロピルトリイソプロポキシシラン、γ－アミノプロピルメチルジメトキシシラン、γ－アミノプロピルメチルジエトキシシラン、γ－（２－アミノエチル）アミノプロピルトリメトキシシラン、γ－（２－アミノエチル）アミノプロピルメチルジメトキシシラン、γ－（２－アミノエチル）アミノプロピルトリエトキシシラン、γ－（２－アミノエチル）アミノプロピルメチルジエトキシシラン、γ－（２－アミノエチル）アミノプロピルトリイソプロポキシシラン、γ－［２－（２－アミノエチル）アミノエチル］アミノプロピルトリメトキシシラン、γ－（６－アミノヘキシル）アミノプロピルトリメトキシシラン、３－（Ｎ－エチルアミノ）－２－メチルプロピルトリメトキシシラン、γ－ウレイドプロピルトリメトキシシラン、γ－ウレイドプロピルトリエトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン、Ｎ－ベンジル－γ－アミノプロピルトリメトキシシラン、Ｎ－ビニルベンジル－γ－アミノプロピルトリエトキシシラン、Ｎ－シクロヘキシルアミノメチルトリエトキシシラン、Ｎ－シクロヘキシルアミノメチルジエトキシメチルシラン、Ｎ－フェニルアミノメチルトリメトキシシラン、（２－アミノエチル）アミノメチルトリメトキシシラン、Ｎ，Ｎ’－ビス［３－（トリメトキシシリル）プロピル］エチレンジアミンなどが挙げられる。 Specific examples of the component (C) include primary amines such as hexylamine, dodecylamine, stearylamine, and secondary amines such as di-n-butylamine, dioctylamine, dilaurylamine, and piperidine. Examples of the tertiary amine include, but are not limited to, triethylamine, tributylamine, trihexylamine and the like. The compound having an amino group and a hydrolyzable silyl group (common name, aminosilane) is not particularly limited, and examples thereof include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisosilane. Propoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- [2- (2- Aminoethyl) aminoethyl] aminopropyl Limethoxysilane, γ- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexyl Examples thereof include aminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and the like.
　また、（Ｃ）成分として第三級アミンとしては、アミジン、グアニジン、ビグアニド、イミダゾール、ジアザビシクロ、ピリジンなどの骨格を含有する化合物が挙げられる。アミジン骨格を有する化合物の具体例としては、アセトアミジン、アミノアセトアミジン、２，２－ジメチルプロピオンアミジンなど、グアニジン骨格を有する化合物の具体例としては、グアニジン、１，１，３，３－テトラメチルグアニジン、１－ブチルグアニジン、１－フェニルグアニジン、１－ｏ－トリルグアニジン、１，３－ジフェニルグアニジン、Ｎ，Ｎ’－ジフェニルグアニジンなど、ビグアニド骨格を有する化合物の具体例としては、ブチルビグアニド、１－ｏ－トリルビグアニドや１－フェニルビグアニドなど、イミダゾール骨格を有する化合物の具体例としては、イミダゾール、２－エチル－４－メチルイミダゾールなど、イミダゾリン骨格を有する化合物としては、２－メチルイミダゾリン、２－ウンデシルイミダゾリン、２－フェニルイミダゾリン、４，４－ジメチル－２－イミダゾリンなど、ジアザビシクロ骨格を有する化合物としては、１，４－ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセン（ＤＢＵ：ジアザビシクロウンデセン）、６－（ジブチルアミノ）－１，８－ジアザビシクロ［５．４．０］－７－ウンデセン（ＤＢＡ－ＤＢＵ）、１，５－ジアザビシクロ［４．３．０］－５－ノネン（ＤＢＮ：ジアザビシクロノネン）等が挙げられる。（これらはジアザビシクロ骨格を有する化合物と総称する。）その他の具体例として、ピリジン、１，３，４，６，７，８－ヘキサヒドロ－２Ｈ－ピリミドピリジン、１，４，５，６－テトラヒドロピジミジン、１，２－ジメチルテトラヒドロピリミジンなどが挙げられるが、これらに限定されるものではない。 In addition, examples of the tertiary amine as the component (C) include compounds containing a skeleton such as amidine, guanidine, biguanide, imidazole, diazabicyclo, and pyridine. Specific examples of the compound having an amidine skeleton include guanidine, 1,1,3,3-tetramethyl such as acetamidine, aminoacetamidine, 2,2-dimethylpropionamidine and the like. Specific examples of compounds having a biguanide skeleton such as guanidine, 1-butylguanidine, 1-phenylguanidine, 1-o-tolylguanidine, 1,3-diphenylguanidine, N, N′-diphenylguanidine include butylbiguanide, 1 Specific examples of compounds having an imidazole skeleton such as -o-tolylbiguanide and 1-phenylbiguanide include imidazole and 2-ethyl-4-methylimidazole. Examples of compounds having an imidazoline skeleton include 2-methylimidazoline, 2- Undecyl imidazoli As compounds having a diazabicyclo skeleton, such as 2-phenylimidazoline and 4,4-dimethyl-2-imidazoline, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,5,7-triaza Bicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1,8-diazabicyclo [5.4. 0] -7-undecene (DBU: diazabicycloundecene), 6- (dibutylamino) -1,8-diazabicyclo [5.4.0] -7-undecene (DBA-DBU), 1,5-diazabicyclo And [4.3.0] -5-nonene (DBN: diazabicyclononene). (These are collectively referred to as compounds having a diazabicyclo skeleton.) Other specific examples include pyridine, 1,3,4,6,7,8-hexahydro-2H-pyrimidopyridine, 1,4,5,6-tetrahydro. Examples thereof include, but are not limited to, pyrimidine and 1,2-dimethyltetrahydropyrimidine.
　前記（Ｃ）成分は、（Ａ）成分１００質量部に対し、０．０１～１０質量部が好ましく、特に好ましくは０．０５～５質量部である。（Ｃ）成分と（Ｂ）成分の添加量は、その比率によっても湿気硬化性と保存安定性に影響を与えるため、（Ｂ）成分と（Ｃ）成分の比率は１：１～１：２０が最も好ましい。 The component (C) is preferably 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the component (A). The addition amount of the component (C) and the component (B) also affects the moisture curability and the storage stability depending on the ratio, so the ratio of the component (B) to the component (C) is 1: 1 to 1:20. Is most preferred.
　本実施形態の硬化性樹脂組成物には、本発明の特性を損なわない範囲において顔料、染料などの着色剤、金属粉、炭酸カルシウム、タルク、シリカ、アモルファスシリカ、アルミナ、水酸化アルミニウム等の無機充填剤、難燃剤、有機充填剤、可塑剤、酸化防止剤、消泡剤、カップリング剤、レベリング剤、レオロジーコントロール剤等の添加剤を適量配合しても良い。これらの添加により樹脂強度・接着強さ・作業性・保存安定性等に優れた組成物およびその硬化物が得られる。 In the curable resin composition of the present embodiment, colorants such as pigments and dyes, metal powder, calcium carbonate, talc, silica, amorphous silica, alumina, aluminum hydroxide and the like are within the range not impairing the characteristics of the present invention. An appropriate amount of additives such as a filler, a flame retardant, an organic filler, a plasticizer, an antioxidant, an antifoaming agent, a coupling agent, a leveling agent, and a rheology control agent may be blended. By these additions, a composition excellent in resin strength, adhesive strength, workability, storage stability, and the like and a cured product thereof can be obtained.
　本発明の第二の実施形態は、分子中に加水分解性シリル基を２以上含有する化合物である（Ａ）成分と、化学式４で示される化合物である（Ｂ）成分と、前記（Ａ）成分を除いたアミン化合物である（Ｃ）成分と、を含む硬化性樹脂組成物である。 In the second embodiment of the present invention, the component (A) which is a compound containing two or more hydrolyzable silyl groups in the molecule, the component (B) which is a compound represented by the chemical formula 4, and the above (A) (C) component which is an amine compound except a component, and a curable resin composition.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　また、本発明の第三の実施形態は、分子中に化学式３の加水分解性シリル基を２以上有する化合物である（Ａ）成分と、化学式５または化学式６で示される化合物またはそれらの混合物である（Ｂ）成分と、前記（Ａ）成分を除いた第二級または第三級アミンである（Ｃ）成分と、を含む硬化性樹脂組成物である。 Moreover, 3rd embodiment of this invention is (A) component which is a compound which has two or more hydrolysable silyl groups of Chemical formula 3 in a molecule | numerator, the compound shown by Chemical formula 5 or Chemical formula 6, or mixtures thereof. A curable resin composition comprising a component (B) and a component (C) which is a secondary or tertiary amine excluding the component (A).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
（式中、Ｘは、それぞれ、アルコキシ基、アミノキシ基、ケトオキシム基、アセトキシ基またはアミノ基である） (Wherein X is an alkoxy group, an aminoxy group, a ketoxime group, an acetoxy group or an amino group, respectively)
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
（式中、Ｒ３は、それぞれ、水素原子またはフッ素原子であり、１～４つのＲ３はフッ素原子である） (Wherein R 3 is a hydrogen atom or a fluorine atom, respectively, and 1 to 4 R 3 are fluorine atoms)
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　本発明の第二の実施形態および第三の実施形態で使用することができる（Ａ）成分としては、例えば、前述した（Ａ）成分を使用することができるが、前記主鎖骨格は同じでも、前記Ｘはそれぞれ独立して反応するため、化学式２と化学式３では硬化後の架橋密度が異なる。これは、化学式２と化学式３におけるＸの数に由来すると推測される。そのため、化学式３を有する（Ａ）成分の方が硬化しやすい傾向が見られる。化学式２を有する（Ａ）成分は、架橋密度を上げるため、塩基性の強い第三級アミンと併用されることが好ましい。 As the component (A) that can be used in the second embodiment and the third embodiment of the present invention, for example, the component (A) described above can be used, but the main chain skeleton is the same. Since X reacts independently of each other, the chemical formula 2 and chemical formula 3 have different crosslinking densities after curing. This is presumed to be derived from the number of X in Chemical Formula 2 and Chemical Formula 3. Therefore, the tendency for the (A) component which has Chemical formula 3 to harden | cured easily is seen. The component (A) having the chemical formula 2 is preferably used in combination with a highly basic tertiary amine in order to increase the crosslinking density.
　本発明の第二の実施形態および第三の実施形態で使用することができる（Ｂ）成分としては、化学式４～化学式６で示される化合物が挙げられる。化学式５において、Ｒ３は水素原子またはフッ素原子を示し、１～４つのＲ３はフッ素原子を含む。（Ｂ）成分が（Ｃ）成分と共に存在することによって、湿気硬化に関する触媒性能が特異的に発現する。また、樹脂成分の溶解性など、取扱いの観点から２５℃で液体であることが好ましい。（Ｂ）成分が化学式６の化合物を含む場合、特に、表面硬化性が向上する傾向にある。 Examples of the component (B) that can be used in the second embodiment and the third embodiment of the present invention include compounds represented by chemical formulas 4 to 6. In Chemical Formula 5, R 3 represents a hydrogen atom or a fluorine atom, and 1 to 4 R 3 include a fluorine atom. When the component (B) is present together with the component (C), the catalyst performance relating to moisture curing is specifically expressed. Moreover, it is preferable that it is a liquid at 25 degreeC from a viewpoint of handling, such as the solubility of a resin component. When the component (B) contains the compound of Chemical Formula 6, the surface curability tends to be improved.
　前記（Ｂ）成分の添加量は、（Ａ）成分１００質量部に対し、０．０１～５．０質量部であることが好ましく、特に好ましくは０．０５～２．０質量部である。前記範囲内である場合は、湿気硬化性が充分発現され、また、保存安定性が安定する傾向にある。 The addition amount of the component (B) is preferably 0.01 to 5.0 parts by mass, particularly preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the component (A). When it is within the above range, moisture curability is sufficiently expressed and the storage stability tends to be stable.
　本実施形態で使用することができる（Ｃ）成分としては、（Ａ）成分以外のアミン化合物である。具体的な（Ａ）成分と（Ｂ）成分の組合せに対して、（Ｃ）成分の具体的な選択が異なる。（Ａ）成分が化学式３で示される基を有し、（Ｂ）成分が化学式４で示される化合物である場合、第一級、第二級、または第三級アミンを使用できる。前記（Ａ）成分が化学式２で示される基を有し、（Ｂ）成分が化学式４で示される化合物である場合、第二級または第三級アミンが適している。（Ａ）成分が化学式３で示される基を有し、（Ｂ）成分が化学式５もしくは化学式６または化学式５と化学式６の混合物である場合、第二級又は第三級アミンが適している。 The component (C) that can be used in the present embodiment is an amine compound other than the component (A). The specific selection of the component (C) differs from the specific combination of the component (A) and the component (B). When the component (A) has a group represented by the chemical formula 3 and the component (B) is a compound represented by the chemical formula 4, a primary, secondary, or tertiary amine can be used. When the component (A) has a group represented by the chemical formula 2 and the component (B) is a compound represented by the chemical formula 4, a secondary or tertiary amine is suitable. When the component (A) has a group represented by the chemical formula 3 and the component (B) is the chemical formula 5 or the chemical formula 6 or a mixture of the chemical formula 5 and the chemical formula 6, a secondary or tertiary amine is suitable.
　前記（Ｃ）成分において、第一級、第二級、または第三級のアミノ基がそれぞれ存在する化合物を使用することはもちろんのこと、一分子中に第一級、第二級、または第三級のアミノ基が混在する化合物を使用することもできる。本実施形態においては、第一級、第二級、または第三級のアミノ基が混在する化合物は、最も大きい級のアミノ基を有するアミン化合物として示すものとする。 In the component (C), a compound having a primary, secondary, or tertiary amino group, respectively, is used, as well as a primary, secondary, or primary compound in one molecule. A compound in which a tertiary amino group is mixed can also be used. In this embodiment, a compound in which a primary, secondary, or tertiary amino group is mixed is shown as an amine compound having the largest amino group.
　前記（Ｃ）成分の具体例としては、例えば、前述した（Ｃ）成分を使用することができる。 As a specific example of the component (C), for example, the component (C) described above can be used.
　前記（Ｃ）成分は、（Ａ）成分１００質量部に対し、０．０１～１０質量部が好ましく、特に好ましくは０．０５～５質量部である。（Ｃ）成分と（Ｂ）成分の添加量は、その比率によっても湿気硬化性と保存安定性に影響を与えるため、（Ｂ）成分と（Ｃ）成分の比率は１：１～１：２０が最も好ましい。 The component (C) is preferably 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the component (A). The addition amount of the component (C) and the component (B) also affects the moisture curability and the storage stability depending on the ratio, so the ratio of the component (B) to the component (C) is 1: 1 to 1:20. Is most preferred.
　本発明の硬化性樹脂組成物には、本発明の特性を損なわない範囲において顔料、染料などの着色剤、金属粉、炭酸カルシウム、タルク、シリカ、アモルファスシリカ、アルミナ、水酸化アルミニウム等の無機充填剤、難燃剤、有機充填剤、可塑剤、酸化防止剤、消泡剤、カップリング剤、レベリング剤、レオロジーコントロール剤等の添加剤を適量配合しても良い。これらの添加により樹脂強度・接着強さ・作業性・保存安定性等に優れた組成物およびその硬化物が得られる。 In the curable resin composition of the present invention, inorganic fillers such as pigments, dyes and other colorants, metal powder, calcium carbonate, talc, silica, amorphous silica, alumina, aluminum hydroxide, etc., are used as long as the characteristics of the present invention are not impaired. Additives such as additives, flame retardants, organic fillers, plasticizers, antioxidants, antifoaming agents, coupling agents, leveling agents, and rheology control agents may be blended in appropriate amounts. By these additions, a composition excellent in resin strength, adhesive strength, workability, storage stability, and the like and a cured product thereof can be obtained.
　次に実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to only these examples.
　［実施例１～１５および比較例１～８］
　硬化性樹脂組成物を調製するために下記成分を準備した。 [Examples 1 to 15 and Comparative Examples 1 to 8]
In order to prepare the curable resin composition, the following components were prepared.
　（Ａ）成分：分子中に化学式２または化学式３の加水分解性シリル基を２以上有する化合物
・分子中に化学式２の加水分解性シリル基を２有して、Ｘがアルコキシ基であり、主鎖がオキシアルキレン骨格と（メタ）アクリル共重合骨格の混合物である化合物（カネカサイリルＭＡ４４０　株式会社カネカ製）
・分子中に化学式３の加水分解性シリル基を２有して、Ｘがアルコキシ基であり、主鎖がオキシアルキレン骨格と（メタ）アクリル共重合骨格の混合物である化合物（カネカサイリルＭＡ４５１　株式会社カネカ製）
　（Ｂ）成分：ピリジン誘導体
・ペンタフルオロピリジン（東京化成工業株式会社製）
・３－クロロ－２，４，５，６－テトラフルオロピリジン（東京化成工業株式会社製）
・３，５－ジクロロ－２，４，６－トリフルオロピリジン（東京化成工業株式会社製）
・２－フルオロピリジン（東京化成工業株式会社製）
・２，６－ジフルオロピリジン（東京化成工業株式会社製）
・２，３，５，６－テトラフルオロピリジン（東京化成工業株式会社製）
　（Ｂ’）成分：（Ｂ）成分以外のフッ素化合物
・ヘキサフルオロプロペンジエチルアミン（東京化成工業株式会社製）
・テトラブチルアンモニウムフルオリド（東京化成工業株式会社製）
・ペンタフルオロフェノール（東京化成工業株式会社製）
　（Ｃ）成分：第一級、第二級、第三級アミン化合物
・テトラメチルグアニジン（第二級アミンと第三級アミンを有する化合物）（東京化成工業株式会社製）
・１，８－ジアザビシクロ［５．４．０］ウンデセン－７（第三級アミンを有する化合物）（ＤＢＵ　サンアプロ株式会社製）
・３－アミノプロピルトリエトキシシラン（第一級アミンを有する化合物）（Ａ－１１００　モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）
　［実施例１６～２５および比較例９～３１］
　硬化性樹脂組成物を調製するために下記成分を準備した。 (A) component: a compound having 2 or more hydrolyzable silyl groups of chemical formula 2 or 3 in the molecule, 2 hydrolyzable silyl groups of chemical formula 2 in the molecule, X being an alkoxy group, Compound whose chain is a mixture of an oxyalkylene skeleton and a (meth) acrylic copolymer skeleton (Kaneka Silyl MA440 manufactured by Kaneka Corporation)
A compound having two hydrolyzable silyl groups of formula 3 in the molecule, X is an alkoxy group, and the main chain is a mixture of an oxyalkylene skeleton and a (meth) acrylic copolymer skeleton (Kanekasilyl MA451 Kaneka Corporation) Made)
Component (B): pyridine derivative / pentafluoropyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 3-Chloro-2,4,5,6-tetrafluoropyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 3,5-dichloro-2,4,6-trifluoropyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 2-Fluoropyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 2,6-Difluoropyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 2,3,5,6-tetrafluoropyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
Component (B ′): Fluorine compound other than component (B), hexafluoropropene diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Tetrabutylammonium fluoride (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Pentafluorophenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
Component (C): primary, secondary, tertiary amine compound / tetramethylguanidine (compound having secondary amine and tertiary amine) (manufactured by Tokyo Chemical Industry Co., Ltd.)
1,8-diazabicyclo [5.4.0] undecene-7 (compound having a tertiary amine) (DBU San Apro Co., Ltd.)
・ 3-Aminopropyltriethoxysilane (compound with primary amine) (A-1100 Momentive Performance Materials Japan GK)
[Examples 16 to 25 and Comparative Examples 9 to 31]
In order to prepare the curable resin composition, the following components were prepared.
　（Ａ）成分：分子中に化学式２または化学式３の加水分解性シリル基を２以上有する化合物
・カネカサイリルＭＡ４４０
・カネカサイリルＭＡ４５１
　（Ｂ）成分：化学式１、化学式４または化学式５で示される化合物
・４－フルオロベンズアルデヒド（東京化成工業株式会社製）
・３，４－ジフルオロベンズアルデヒド（東京化成工業株式会社製）
・３，４，５－トリフルオロベンズアルデヒド（東京化成工業株式会社製）
・２，３，４，５－テトラフルオロベンズアルデヒド（東京化成工業株式会社製）
・ペンタフルオロベンズアルデヒド（東京化成工業株式会社製）
・ペンタフルオロベンゼンチオール（東京化成工業株式会社製）
　（Ｂ’）成分：（Ｂ）成分以外のフッ素化合物や塩素化合物
・ペンタフルオロフェノール（東京化成工業株式会社製）
・ペンタフルオロアニリン（東京化成工業株式会社製）
・ペンタフルオロフェニルヒドラジン（東京化成工業株式会社製）
・ペンタフルオロトリブチルアミン（東京化成工業株式会社製）
・ペンタフルオロトリエチルアミン（東京化成工業株式会社製）
・ペンタフルオロ安息香酸（東京化成工業株式会社製）
・２－クロロベンズアルデヒド（東京化成工業株式会社製）
・２，６－ジクロロベンズアルデヒド（東京化成工業株式会社製）
　（Ｃ）成分：第一級、第二級、第三級アミン化合物
・ＤＢＵ（第三級アミンを有する化合物）
・テトラメチルグアニジン（第二級アミンと第三級アミンを有する化合物）
・Ａ－１１００（第一級アミンを有する化合物）
　製造方法は、プラスチック容器中に（Ａ）成分に（Ｂ）成分を計量し、自転・公転真空ミキサーを用いて１分間混錬した。さらに（Ｃ）成分を計量し、前記ミキサーを用いて更に１分間混錬して硬化性樹脂組成物を得た。得られた硬化性樹脂組成物は、それぞれ密閉容器に充填して２３℃で２４時間静置した。詳細な調製量は表１～３に従い、数値は全て質量部で表記する。 Component (A): Compound / Kanekasilyl MA440 having two or more hydrolyzable silyl groups of Chemical Formula 2 or Chemical Formula 3 in the molecule
・ Kaneka Silyl MA451
Component (B): Compound represented by Chemical Formula 1, Chemical Formula 4 or Chemical Formula 5, 4-fluorobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 3,4-Difluorobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 3,4,5-trifluorobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 2,3,4,5-Tetrafluorobenzaldehyde (Tokyo Chemical Industry Co., Ltd.)
・ Pentafluorobenzaldehyde (Tokyo Chemical Industry Co., Ltd.)
・ Pentafluorobenzenethiol (manufactured by Tokyo Chemical Industry Co., Ltd.)
Component (B ′): Fluorine compound or chlorine compound other than component (B), pentafluorophenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Pentafluoroaniline (Tokyo Chemical Industry Co., Ltd.)
・ Pentafluorophenylhydrazine (Tokyo Chemical Industry Co., Ltd.)
・ Pentafluorotributylamine (Tokyo Chemical Industry Co., Ltd.)
・ Pentafluorotriethylamine (Tokyo Chemical Industry Co., Ltd.)
・ Pentafluorobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 2-Chlorobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 2,6-Dichlorobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.)
Component (C): primary, secondary, tertiary amine compound / DBU (compound having tertiary amine)
・ Tetramethylguanidine (compound having secondary and tertiary amines)
A-1100 (compound having a primary amine)
In the production method, the component (B) was weighed into the component (A) in a plastic container and kneaded for 1 minute using a rotation / revolution vacuum mixer. Furthermore, (C) component was measured and knead | mixed for 1 minute using the said mixer, and the curable resin composition was obtained. The obtained curable resin composition was filled in an airtight container and allowed to stand at 23 ° C. for 24 hours. Detailed preparation amounts follow Tables 1 to 3, and all numerical values are expressed in parts by mass.
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
　実施例１～２５および比較例１～３１に対して、外観、表面硬化性および深部硬化性について試験項目を実施した。また、初期の試験項目を測定した後、保存安定性を確認するため７０℃雰囲気にて５日間放置した後の各試験項目を測定した。その結果を表４および表５に示す。 Test items were carried out for Examples 1 to 25 and Comparative Examples 1 to 31 with respect to appearance, surface curability, and deep part curability. In addition, after measuring initial test items, each test item was measured after being left in a 70 ° C. atmosphere for 5 days to confirm storage stability. The results are shown in Tables 4 and 5.
　［外観確認］
硬化性樹脂組成物を幅１０ｍｍ×長５０ｍｍのビート状にポリエチレンシート上へ塗布した時の粘性を以下の通り三段階評価を行い、「性状」として示す。外観確認における性状は、「低粘度」であることが好ましい。 [Appearance check]
The viscosity when the curable resin composition is applied onto a polyethylene sheet in a beat shape having a width of 10 mm and a length of 50 mm is evaluated in the following three stages, and is shown as “property”. The property in the appearance confirmation is preferably “low viscosity”.
　低粘度：塗布しやすい程度に粘度が低い
　高粘度：塗布しにくい程度の高粘度であるが塗布はできる
　ゲル状：ゲル化が進行して半固体状態になっているため塗布できない　
　［表面硬化性確認］
　２３℃×５０％ＲＨ雰囲気下で、硬化性樹脂組成物をポリエチレンシート上に幅１０ｍｍ×厚１ｍｍ×長５０ｍｍのビートを塗布し、爪楊枝で組成物の表面を軽く触れる。組成物を塗布してから、爪楊枝に付着せずに表面が硬化したと判断されるまでの時間を「皮張り時間（分）」として表面硬化性を評価した。２４時間以上放置しても硬化しない場合は、「未硬化」と表記する。皮張り時間は、２０分以内であることが好ましい。数値は分で表記する。 Low viscosity: low enough to be easily applied High viscosity: high viscosity that is difficult to apply, but can be applied Gel: cannot be applied because gelation has progressed to a semi-solid state
[Surface Curability Check]
Under a 23 ° C. × 50% RH atmosphere, a beet having a width of 10 mm × thickness 1 mm × length 50 mm is applied on a polyethylene sheet, and the surface of the composition is lightly touched with a toothpick. The time from the application of the composition to the time when it was determined that the surface was cured without adhering to the toothpick was evaluated as the “skinning time (minutes)”. When it is not cured even after being left for 24 hours or more, it is described as “uncured”. The skinning time is preferably within 20 minutes. Numbers are expressed in minutes.
　［深部硬化性確認］
　表面硬化性確認で塗布した硬化性樹脂組成物を更に２４時間放置した後、深部硬化性の硬化状態を評価した。硬化状態は以下の通り三段階評価を行い、その結果を「深部硬化状態」とする。深部硬化状態は、「硬化」の状態であることが好ましい。 [Deep part curability check]
The curable resin composition applied in the confirmation of surface curability was further allowed to stand for 24 hours, and then the deep curable cured state was evaluated. The cured state is evaluated in three stages as follows, and the result is defined as a “deep cured state”. The deep cured state is preferably a “cured” state.
　硬化：表面から深部まで均一に硬化している
　ゲル化：表面よりも深部の方の硬化が不十分である
　未硬化：表面および深部が硬化していない
　［保存安定性確認］
　硬化性樹脂組成物の調整後の初期特性を確認した後、保存安定性を確認するために容器を７０℃雰囲気にて５日間放置する。放置後に、硬化性樹脂組成物における外観、表面硬化性、深部硬化性について再確認を行った。 Curing: Cured uniformly from the surface to the deep part Gelation: Insufficient curing in the deeper part than the surface Uncured: The surface and deep part are not cured [Confirm storage stability]
After confirming the initial characteristics after adjustment of the curable resin composition, the container is left in a 70 ° C. atmosphere for 5 days in order to confirm the storage stability. After standing, reconfirmation was performed about the external appearance, surface curability, and deep part curability in the curable resin composition.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
　［実施例２６］
　実施例１５に対して充填剤として重質炭酸カルシウムを加えた組成物について、粘度、表面硬化性、引張剪断接着強さ１および引張剪断接着強さ２について測定を行った。さらに、保存安定性を確認するため７０℃雰囲気にて５日間放置した後の各試験項目を測定した。その結果を表６に示す。 [Example 26]
The composition obtained by adding heavy calcium carbonate as a filler to Example 15 was measured for viscosity, surface curability, tensile shear bond strength 1 and tensile shear bond strength 2. Furthermore, in order to confirm the storage stability, each test item after being left in a 70 ° C. atmosphere for 5 days was measured. The results are shown in Table 6.
　［実施例２７］
　実施例２４に対して行ったことを除いては、実施例２６と同様の測定を行った。その結果を表７に示す。 [Example 27]
The same measurement as in Example 26 was performed, except that the measurement was performed on Example 24. The results are shown in Table 7.
　製造方法は、プラスチック容器中に（Ａ）成分と充填剤を計量し、自転・公転真空ミキサーを用いて１分間混錬した。次に（Ｃ）成分の１，８－ジアザビシクロ［５．４．０］ウンデセン－７を計量して１分間混錬後、（Ｂ）成分を計量して１分間混錬した。さらに（Ｃ）成分の３－アミノプロピルトリエトキシシランを計量して前記ミキサーを用いて更に１分間混錬して硬化性樹脂組成物を得た。得られた硬化性樹脂組成物は、密閉容器に充填して２３℃で２４時間静置した。詳細な調製量は表６または表７に従い、数値は全て質量部で表記する。 In the production method, the component (A) and the filler were weighed in a plastic container and kneaded for 1 minute using a rotation / revolution vacuum mixer. Next, 1,8-diazabicyclo [5.4.0] undecene-7 as component (C) was weighed and kneaded for 1 minute, and then component (B) was weighed and kneaded for 1 minute. Further, 3-aminopropyltriethoxysilane as component (C) was weighed and kneaded for 1 minute using the mixer to obtain a curable resin composition. The obtained curable resin composition was filled in a sealed container and allowed to stand at 23 ° C. for 24 hours. Detailed preparation amounts are in accordance with Table 6 or Table 7, and all numerical values are expressed in parts by mass.
　［粘度測定］
　コーンプレート型回転粘度計を用いて、２５℃で３分後の粘度を測定した。測定結果を「粘度（Ｐａ・ｓ）」とする。粘度は充填剤の添加量により適宜設定されるため、特に好ましい範囲は無い。 [Viscosity measurement]
The viscosity after 3 minutes at 25 ° C. was measured using a cone plate type rotational viscometer. The measurement result is “viscosity (Pa · s)”. Since the viscosity is appropriately set depending on the amount of filler added, there is no particularly preferred range.
　［引張剪断接着強さ測定］
　長１００ｍｍ×幅２５ｍｍ×厚１ｍｍの寸法のテストピースを使用し、接着面積が２５ｍｍ×１０ｍｍになる様に実施例２６を塗布して貼り合わせて固定治具で固定する。その後、２５℃×５０％ＲＨ雰囲気にて７日間放置する。ＪＩＳ　Ｋ　６８５０に準拠して最大の剪断強度を測定し、接着面積より「剪断接着強さ（ＭＰａ）」を計算した。テストピースとして、アルミニウムを使用した場合を「剪断接着強さ１」とし、ポリカーボネートを使用した場合を「剪断接着強さ２」とする。剪断接着強さ１に関しては３．０ＭＰａ以上、剪断接着強さ２に関しては２．０ＭＰａ以上の数値を発現していれば、接着用途でも使用することができる。 [Measurement of tensile shear bond strength]
Using a test piece having dimensions of 100 mm long × 25 mm wide × 1 mm thick, Example 26 is applied and bonded so that the bonding area is 25 mm × 10 mm, and fixed with a fixing jig. Then, it is left for 7 days in an atmosphere of 25 ° C. × 50% RH. The maximum shear strength was measured in accordance with JIS K 6850, and “shear bond strength (MPa)” was calculated from the adhesion area. When aluminum is used as the test piece, “shear bond strength 1” is set, and when polycarbonate is used, “shear bond strength 2” is set. As long as a value of 3.0 MPa or more is expressed for the shear bond strength 1 and 2.0 MPa or more is expressed for the shear bond strength 2, it can be used for bonding applications.
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
　実施例７、比較例１および２を比較すると、（Ｂ）成分が含まれない場合や（Ｃ）成分が含まれない場合には、湿気硬化性が非常に遅く、（Ｂ）成分と（Ｃ）成分を両方添加した組成物は特異的に早い湿気硬化性を有すると共に、保存安定性を有する。また、実施例２と比較例３～５を比較すると、比較例３～５は（Ｂ）成分の代わりになるハロゲン化合物を添加している。比較例３においては表面硬化性が低下し、比較例４では性状が悪化し、比較例５では表面硬化性および深部硬化性が低下している。この様に、ハロゲン化合物と（Ｃ）成分を組み合わせるだけでは、本発明の湿気硬化性および保存安定性を両立することは困難である。一般的に、充填剤を添加した湿気硬化性は湿気の浸透が遅くなるため表面硬化性および深部硬化性が低下する傾向にあるが、実施例１５と実施例２６では、表面硬化性の低下は若干見られるものの、充分な硬化性が確保されている。 When Example 7 and Comparative Examples 1 and 2 are compared, when the component (B) is not included or when the component (C) is not included, the moisture curability is very slow, and the component (B) and the component (C) ) The composition to which both components are added has a particularly fast moisture-curing property and storage stability. Further, when Example 2 is compared with Comparative Examples 3 to 5, Comparative Examples 3 to 5 add a halogen compound in place of the component (B). In Comparative Example 3, the surface curability is lowered, in Comparative Example 4, the properties are deteriorated, and in Comparative Example 5, the surface curability and the deep part curability are lowered. Thus, it is difficult to achieve both the moisture curability and the storage stability of the present invention only by combining the halogen compound and the component (C). In general, the moisture curable with the filler added tends to decrease the surface curable property and the deep curable property due to the slow penetration of moisture, but in Examples 15 and 26, the decrease in surface curable property is Although slightly seen, sufficient curability is ensured.
　実施例２０～２４から化学式４の（Ｂ）成分を使用することで（Ａ）成分の加水分解性シリル基が化学式２または化学式３に依存することなく、また（Ｃ）成分の種類に依存することなく良好な表面硬化性を有する。さらに、実施例２０～２４に係る組成物は７０℃雰囲気に放置してもその特性が変わることが無く、保存安定性も有している。また、湿気硬化性組成物全般の傾向として充填剤を添加すると外気の湿気が浸透し難くなるため、表面硬化性および深部硬化性が低下する傾向が見られる。しかし、実施例２７では、表面硬化性が若干低下したが使用に際しては問題無い程度で表面硬化性を維持している。また、実施例２５と比較例１６を比較すると、化学式６の（Ｂ）成分を使用することで表面硬化性が向上することがわかる。さらに、実施例１６～１９および２５と比較例９～１５を比較すると判る通り、化学式５または化学式６の（Ｂ）成分を使用した場合は特定の（Ａ）成分および（Ｃ）成分を選定すると特異的に性能が向上する。具体的には（Ａ）成分として加水分解性シリル基が化学式３であり、（Ｃ）成分が第二級および／または第三級アミンであれば特異的に良好な硬化性および保存性を発現する。さらに、実施例１６～１９および２５と比較例１９～３１と比較すると、本発明における（Ｂ）成分を使用することで硬化性組成物は特異的に硬化性および保存安定性が発現することがわかる。 By using the component (B) of the chemical formula 4 from Examples 20 to 24, the hydrolyzable silyl group of the component (A) does not depend on the chemical formula 2 or 3, and depends on the type of the component (C). And has good surface curability. Further, the compositions according to Examples 20 to 24 do not change their properties even when left in an atmosphere at 70 ° C., and have storage stability. Further, as a general tendency of the moisture curable composition, when the filler is added, it becomes difficult for the moisture of the outside air to permeate, so that the surface curability and the deep curability tend to decrease. However, in Example 27, the surface curability was slightly lowered, but the surface curability was maintained to the extent that there was no problem in use. Moreover, when Example 25 and Comparative Example 16 are compared, it turns out that surface curability improves by using (B) component of Chemical formula 6. FIG. Further, as can be seen from the comparison between Examples 16 to 19 and 25 and Comparative Examples 9 to 15, when the component (B) of the chemical formula 5 or 6 is used, the specific component (A) and component (C) are selected. Performance improves specifically. Specifically, if the hydrolyzable silyl group is the chemical formula 3 as the component (A) and the component (C) is a secondary and / or tertiary amine, it exhibits particularly good curability and storage stability. To do. Further, when compared with Examples 16 to 19 and 25 and Comparative Examples 19 to 31, the use of the component (B) in the present invention indicates that the curable composition exhibits specific curability and storage stability. Recognize.
　電気業界では、環境対策の一環として部材における錫含有率を低下させる規制が進みつつある。湿気硬化性を有する硬化性樹脂には有機錫化合物が長年汎用的に使用されているため、有機錫化合物を使用せずに、同等の湿気硬化性を発現するためには技術的なハードルが高い。本発明は、有機錫化合物を使用しない有力な技術であり、電気分野にとらわれず自動車分野などの他分野にも展開することが出来る。また、本発明の（Ｂ）成分添加量は触媒量であり、ハロゲンの問題に対しても有用な技術である。 In the electrical industry, regulations that reduce the tin content in components are advancing as part of environmental measures. Since organic tin compounds have been widely used for curable resins with moisture-curing properties for many years, technical hurdles are high in order to develop equivalent moisture-curing properties without using organic tin compounds. . The present invention is an effective technique that does not use an organic tin compound, and can be applied to other fields such as the automobile field without being limited to the electric field. In addition, the amount of component (B) added in the present invention is a catalytic amount, which is a useful technique for the problem of halogen.

Claims (14)

  1. 　分子中に加水分解性シリル基を２以上含有する化合物である（Ａ）成分と、
    　化学式１で示される化合物である（Ｂ）成分と、
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１は、それぞれ、水素原子、フッ素原子または塩素原子であり、Ｒ１の少なくとも１つはフッ素原子である）
    　前記（Ａ）成分および（Ｂ）成分を除いたアミン化合物である（Ｃ）成分と、を含む硬化性樹脂組成物。     (A) component which is a compound containing two or more hydrolyzable silyl groups in the molecule;
    (B) component which is a compound shown by Chemical formula 1,
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 is a hydrogen atom, a fluorine atom or a chlorine atom, respectively, and at least one of R 1 is a fluorine atom)
    (C) component which is an amine compound except said (A) component and (B) component, and curable resin composition.
  2. 　前記（Ａ）成分の１以上の加水分解性シリル基が化学式２で示される基であり、
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ２は置換または非置換の炭素数１～２０の炭化水素基を示し、Ｘは、それぞれ、アルコキシ基、アミノキシ基、ケトオキシム基、アセトキシ基またはアミノ基である）
    　前記（Ｃ）成分のアミン化合物が第三級アミンであることを特徴とする、請求項１に記載の硬化性樹脂組成物。     One or more hydrolyzable silyl groups of the component (A) are groups represented by the chemical formula 2,
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 2 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and X is an alkoxy group, an aminoxy group, a ketoxime group, an acetoxy group or an amino group, respectively)
    The curable resin composition according to claim 1, wherein the amine compound as the component (C) is a tertiary amine.
  3. 　前記第三級アミンが、アミジン骨格を有する化合物、グアニジン骨格を有する化合物、またはジアザビシクロ骨格を有する化合物の１以上であることを特徴とする、請求項２に記載の硬化性樹脂組成物。 The curable resin composition according to claim 2, wherein the tertiary amine is one or more of a compound having an amidine skeleton, a compound having a guanidine skeleton, or a compound having a diazabicyclo skeleton.
  4. 　前記（Ａ）成分の１以上の加水分解性シリル基が化学式３で示される基であり、
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｘは、それぞれ、アルコキシ基、アミノキシ基、ケトオキシム基、アセトキシ基またはアミノ基である）
    　前記（Ｃ）成分のアミン化合物が第一級、第二級または第三級アミンであることを特徴とする、請求項１に記載の硬化性樹脂組成物。     One or more hydrolyzable silyl groups of the component (A) are groups represented by the chemical formula 3,
    Figure JPOXMLDOC01-appb-C000003
     (Wherein X is an alkoxy group, an aminoxy group, a ketoxime group, an acetoxy group or an amino group, respectively)
    The curable resin composition according to claim 1, wherein the amine compound as the component (C) is a primary, secondary, or tertiary amine.
  5. 　前記第一級、第二級または第三級アミンが、アミノ基と加水分解性シリル基を有する化合物、アミジン骨格を有する化合物、グアニジン骨格を有する化合物、またはジアザビシクロ骨格を有する化合物を１以上含有することを特徴とする、請求項４に記載の硬化性樹脂組成物。 The primary, secondary or tertiary amine contains at least one compound having an amino group and a hydrolyzable silyl group, a compound having an amidine skeleton, a compound having a guanidine skeleton, or a compound having a diazabicyclo skeleton. The curable resin composition according to claim 4, wherein
  6. 　分子中に加水分解性シリル基を２以上含有する化合物である（Ａ）成分と、 
    　化学式４で示される化合物である（Ｂ）成分と、
    Figure JPOXMLDOC01-appb-C000004
     　前記（Ａ）成分を除いたアミン化合物である（Ｃ）成分と、を含む硬化性樹脂組成物。     (A) component which is a compound containing two or more hydrolyzable silyl groups in the molecule;
    (B) component which is a compound shown by Chemical formula 4,
    Figure JPOXMLDOC01-appb-C000004
     (C) component which is an amine compound except the said (A) component, The curable resin composition containing.
  7. 　前記（Ａ）成分の１以上の加水分解性シリル基が化学式３で示される基であることを特徴とする、請求項６に記載の硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｘは、それぞれ、アルコキシ基、アミノキシ基、ケトオキシム基、アセトキシ基またはアミノ基である）     The curable resin composition according to claim 6, wherein one or more hydrolyzable silyl groups of the component (A) are groups represented by Chemical Formula 3.
    Figure JPOXMLDOC01-appb-C000005
     (Wherein X is an alkoxy group, an aminoxy group, a ketoxime group, an acetoxy group or an amino group, respectively)
  8. 　前記アミン化合物が、アミノ基と加水分解性シリル基を有する化合物、アミジン骨格を有する化合物、グアニジン骨格を有する化合物、またはジアザビシクロ骨格を有する化合物を１以上含有する化合物であることを特徴とする、請求項６または７に記載の硬化性樹脂組成物。 The amine compound is a compound having at least one compound having an amino group and a hydrolyzable silyl group, a compound having an amidine skeleton, a compound having a guanidine skeleton, or a compound having a diazabicyclo skeleton, Item 8. The curable resin composition according to Item 6 or 7.
  9. 　前記（Ａ）成分の１以上の加水分解性シリル基が化学式２で示される基であり、
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｒ２は置換または非置換の炭素数１～２０の炭化水素基を示し、Ｘは、それぞれアルコキシ基、アミノキシ基、ケトオキシム基、アセトキシ基またはアミノ基である）
    　前記（Ｃ）成分のアミン化合物が第二級または第三級アミンであることを特徴とする、請求項６に記載の硬化性樹脂組成物。     One or more hydrolyzable silyl groups of the component (A) are groups represented by the chemical formula 2,
    Figure JPOXMLDOC01-appb-C000006
     (Wherein R 2 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and X is an alkoxy group, an aminoxy group, a ketoxime group, an acetoxy group or an amino group, respectively)
    The curable resin composition according to claim 6, wherein the amine compound as the component (C) is a secondary or tertiary amine.
  10. 　前記第二級または第三級アミンが、アミジン骨格を有する化合物、グアニジン骨格を有する化合物、またはジアザビシクロ骨格を有する化合物を１以上含有する化合物であることを特徴とする、請求項９に記載の硬化性樹脂組成物。 The curing according to claim 9, wherein the secondary or tertiary amine is a compound having at least one compound having an amidine skeleton, a compound having a guanidine skeleton, or a compound having a diazabicyclo skeleton. Resin composition.
  11. 　分子中に化学式３の加水分解性シリル基を２以上有する化合物である（Ａ）成分と、
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ｘは、それぞれ、アルコキシ基、アミノキシ基、ケトオキシム基、アセトキシ基またはアミノ基である）
    　化学式５または化学式６で示される化合物である（Ｂ）成分と、
    Figure JPOXMLDOC01-appb-C000008
     （式中、Ｒ３は、それぞれ、水素原子またはフッ素原子であり、１～４つのＲ３はフッ素原子である）
    Figure JPOXMLDOC01-appb-C000009
     　前記（Ａ）成分を除いた第二級または第三級アミンである（Ｃ）成分と、を含む硬化性樹脂組成物。     (A) component which is a compound having two or more hydrolyzable silyl groups of chemical formula 3 in the molecule;
    Figure JPOXMLDOC01-appb-C000007
     (Wherein X is an alkoxy group, an aminoxy group, a ketoxime group, an acetoxy group or an amino group, respectively)
    (B) component which is a compound represented by Chemical Formula 5 or Chemical Formula 6,
    Figure JPOXMLDOC01-appb-C000008
     (Wherein R 3 is a hydrogen atom or a fluorine atom, respectively, and 1 to 4 R 3 are fluorine atoms)
    Figure JPOXMLDOC01-appb-C000009
     (C) component which is a secondary or tertiary amine except the said (A) component, and curable resin composition containing.
  12. 　前記第二級または第三級アミンが、アミジン骨格を有する化合物、グアニジン骨格を有する化合物、またはジアザビシクロ骨格を有する化合物を１以上含有する化合物であることを特徴とする、請求項１１に記載の硬化性樹脂組成物。 The curing according to claim 11, wherein the secondary or tertiary amine is a compound having an amidine skeleton, a compound having a guanidine skeleton, or a compound having one or more compounds having a diazabicyclo skeleton. Resin composition.
  13. 　前記加水分解性シリル基がアルコキシ基を含有することを特徴とする、請求項１～１２のいずれか１項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 12, wherein the hydrolyzable silyl group contains an alkoxy group.
  14. 　前記（Ａ）成分の主鎖が、（メタ）アクリルモノマー重合体および／またはオキシアルキレン重合体からなる請求項１～１３のいずれか１項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 13, wherein the main chain of the component (A) comprises a (meth) acrylic monomer polymer and / or an oxyalkylene polymer.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0733993A (en) * 1993-07-16 1995-02-03 Kanegafuchi Chem Ind Co Ltd Curable resin composition
JPH07145325A (en) * 1993-11-25 1995-06-06 Dainippon Ink & Chem Inc Curable composition
JP2005336401A (en) * 2004-05-28 2005-12-08 Cemedine Co Ltd Curable composition
JP2007039568A (en) * 2005-08-03 2007-02-15 Yokohama Rubber Co Ltd:The Curable composition
WO2007077888A1 (en) * 2005-12-28 2007-07-12 Kaneka Corporation Curable composition
JP2010077226A (en) * 2008-09-24 2010-04-08 Konishi Co Ltd Curable resin composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0733993A (en) * 1993-07-16 1995-02-03 Kanegafuchi Chem Ind Co Ltd Curable resin composition
JPH07145325A (en) * 1993-11-25 1995-06-06 Dainippon Ink & Chem Inc Curable composition
JP2005336401A (en) * 2004-05-28 2005-12-08 Cemedine Co Ltd Curable composition
JP2007039568A (en) * 2005-08-03 2007-02-15 Yokohama Rubber Co Ltd:The Curable composition
WO2007077888A1 (en) * 2005-12-28 2007-07-12 Kaneka Corporation Curable composition
JP2010077226A (en) * 2008-09-24 2010-04-08 Konishi Co Ltd Curable resin composition

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