JP2005179387A - Curable composition and sealing material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a useful readily producible curable composition curable with moisture in the open air, etc., affording a rubber-like elastic body having especially excellent weather resistance while maintaining excellent operation efficiency and physical properties after curing and having a wide range of application to a sealing material, an adhesive, a coating, etc. <P>SOLUTION: The curable composition and sealing material composition comprise an acrylic and/or a methacrylic polymer (A) containing a cross-linkable silyl group and a polymerizable unsaturated group and, as necessary, further a cross-linkable silyl group-containing organic polymer (B) other than the polymer (A) as curing components. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable composition and a sealing material composition that are cured by moisture in the air or the like to become a rubber-like elastic body excellent in weather resistance and various physical properties.

  Conventionally, it is generally called a modified silicone resin as a moisture-curing resin component used in curable compositions such as waterproof sealants for buildings, civil engineering, and automobiles, adhesives, and paints. Resins and polyurethane resins whose chains are polyethers or aliphatic hydrocarbon polymers and contain crosslinkable silyl groups in the molecule are widely used because of their excellent workability and adhesiveness.

  However, in recent years, in the fields of buildings, civil engineering, automobiles, etc., there has been a growing need for maintaining the performance over a long period of time, so-called longevity, and also for sealing materials, adhesives, paints, etc. used in these. Further improvements in durability such as adhesion and heat resistance, water resistance, and weather resistance are required. Sealing materials, adhesives and paints containing crosslinkable silyl group-containing resins such as polyether-based modified silicone resins (crosslinkable silyl group-containing polyoxyalkylene polymers) and crosslinkable silyl group-containing aliphatic hydrocarbon polymers In such cases, workability and adhesion are good, but there is a disadvantage that the elongation and weather resistance after curing are still insufficient and inferior in durability, and furthermore, special equipment is required for synthesis of modified silicone resin, There is a problem that it is difficult and expensive to manufacture.

Moreover, using a photocurable compound together as a method of improving a weather resistance is proposed. For example, a method of blending a photocurable compound and a tertiary amine-containing hindered amine light stabilizer into a reactive silicon group-containing organic polymer has been disclosed (see Patent Document 1), but this method has some weather resistance. Although improved, it is still inadequate. Furthermore, secondary amine-containing hindered amine light stabilizers, other primary or secondary amine compounds or aminosilane coupling agents, etc. were used as curing accelerators and adhesion promoters. In such a case, the active hydrogen of the amine compound is easily subjected to Michael addition reaction to the unsaturated group of the photocurable compound, so that the effect of improving the weather resistance is remarkably impaired or the viscosity increases during storage. .
JP 05-70531 A

  The present invention solves the problems of the prior art, is easy to manufacture, is cured by moisture in the atmosphere, etc., and particularly has excellent weather resistance while maintaining excellent workability and physical properties after curing. An object of the present invention is to provide a useful curable composition having a wide range of applications, such as a sealing material, an adhesive, and a paint, which is an excellent rubbery elastic body.

In order to achieve the above-mentioned object, the present inventors have intensively studied. As a result, in order to make the weather resistance excellent, an acrylic and / or methacrylic group containing a crosslinkable silyl group and a polymerizable unsaturated group in the molecule. The inventors have found that the above problems can be solved by using a polymer, and have reached the present invention.
That is, the present invention includes the following (1) to (8).

(1) A curable composition comprising a crosslinkable silyl group and a polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (A) as a curing component.

(2) containing a crosslinkable silyl group and a polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (A) and other crosslinkable silyl group-containing organic polymer (B) as a curing component, A curable composition characterized by the above.

(3) The crosslinkable silyl group and polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (A) are crosslinkable with the hydroxyl and polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (a). The curable composition according to the above (1) or (2), which is a reaction product with the silyl group-containing isocyanate compound (b).

(4) The hydroxyl group and polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (a) is an ethylenically unsaturated compound containing a hydroxyl group-containing acrylic and / or methacrylic monomer at 50 to 300 ° C. Obtained by radical copolymerization reaction, the number average molecular weight is 500 to 50,000, Tg is 0 ° C. or less, the viscosity at 25 ° C. is 100,000 mPa · s or less, and a hydroxyl group and a polymerizable unsaturated group are contained in the molecule. The curable composition according to (3), which is an acrylic and / or methacrylic copolymer to be contained.

(5) The total degree of unsaturation measured by a method for determining the hydroxyl group and polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (a) by the Wijs method is 0.01 meq / g or more (3 ) Or (4) curable composition.

(6) The curable composition according to (2), wherein the crosslinkable silyl group-containing organic polymer (B) is a crosslinkable silyl group-containing polyoxyalkylene polymer.

(7) The curable composition according to any one of (1) to (6), further containing an additive.

(8) A sealing material composition comprising a crosslinkable silyl group and a polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (A) as a curing component.

  The curable composition of the present invention is easy to manufacture, is cured by moisture in the atmosphere and becomes a rubber-like elastic body having a low modulus and extremely large elongation while maintaining excellent weather resistance, such as adhesion and workability. In addition, because it is excellent in weather resistance, for example, when used as a sealing material, the appearance and elongation are improved to significantly improve the waterproofing effect, extending the life and performance of recent buildings, civil engineering, automobiles, etc. Can adapt well.

The present invention will be described in detail below.
The crosslinkable silyl group and polymerizable unsaturated group-containing acrylic and / or methacrylic (hereinafter, “acrylic and / or methacrylic” is referred to as (meth) acrylic) polymer (A) in the present invention is the main chain of the polymer. Is a polymer obtained by radical polymerization or copolymerization of an ethylenically unsaturated compound containing a (meth) acrylic monomer as a main component, and the polymer main chain is a crosslinkable silyl compound represented by the following general formula (1) Group and a polymerizable unsaturated group, a crosslinkable silyl group reacts with moisture (water), hydrolyzes to form a silanol group, and then the silanol groups dehydrate and condense together to form a siloxane bond (-SiOSi-) is formed, crosslinked and cured. By using this crosslinkable silyl group and polymerizable unsaturated group-containing (meth) acrylic polymer (A) as a curing component, the weather resistance after curing of the resulting curable composition is remarkably improved. .

（式中、Ｒは炭化水素基であり、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基が好ましく、メチル基が最も好ましい。Ｘで示される反応性基はハロゲン原子、水素原子、水酸基、アルコキシ基、アシルオキシ基、ケトキシメート基、アミド基、酸アミド基、メルカプト基、アルケニルオキシ基及びアミノオキシ基より選ばれる基であり、Ｘが複数の場合には、Ｘは同じ基であっても異なった基であってもよい。このうちＸはアルコキシ基が好ましく、メトキシ基が最も好ましい。ａは０、１又は２の整数であり、０又は１が最も好ましい。）
なお、この著しく耐候性を向上させる効果は、（メタ）アクリル系重合体部分が元来耐候性の良いことに加えて、硬化物の表面が長時間太陽光に暴露されたとき、含有される重合性不飽和基が光により反応や重合をして、硬化物表面の架橋を増加させることにより更に耐候性を向上させることによるものと推察される。
前記重合体（Ａ）において架橋性シリル基と重合性不飽和基の存在する位置はそれぞれ重合体主鎖の末端あるいは主鎖中のどのような位置であっても良い。架橋性シリル基の個数は分子中に平均０．１個以上、更に０．４〜６個、特に０．４〜３個含有されるのが好ましい。架橋性シリル基が０．１個未満の場合は硬化が不十分となりやすく好ましくない。
また、前記の重合性不飽和基は太陽光等の光で反応や重合するものであればどのようなものでも良いが、前記の（メタ）アクリル系単量体を主成分とするエチレン性不飽和化合物をラジカル重合又は共重合した際に重合性不飽和基が残存して含有されたものが好ましい。前記重合体（Ａ）中の重合性不飽和基の含有量は総不飽和度として示され、その総不飽和度は後述のＷｉｊｓ法（ウィイス法）による定量方法により測定した値が０．０１ｍｅｑ／ｇ以上、特に０．０１〜２ｍｅｑ／ｇのものが最も好ましい。また、前記重合体（Ａ）はゲルパーミエーションクロマトグラフィーによるポリスチレン換算の数平均分子量が１，０００〜５０，０００、更に１，０００〜３０，０００、特に１，０００〜１０，０００のもの、２５℃における粘度が１００，０００ｍＰａ・ｓ以下、特に５０，０００ｍＰａ・ｓ以下であることが好ましい。総不飽和度が０．０１ｍｅｑ／ｇ未満の場合は耐候性を向上させる効果が不十分となり、数平均分子量が５０，０００を、２５℃における粘度が１００，０００ｍＰａ・ｓをそれぞれ超えると硬化性組成物の作業性が悪くなる。また、前記重合体（Ａ）の特徴として、重合性不飽和基の含有量が少量でかつ高分子量であるため、２級アミンによるマイケル付加反応が起き難く、例えばヒンダード２級アミン系の酸化防止剤を使用しても、得られる硬化性組成物の貯蔵安定性が良好なことが挙げられる。

Wherein R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and most preferably a methyl group. The reactive group is a group selected from a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group, and an aminooxy group. In this case, X may be the same group or different groups, among which X is preferably an alkoxy group, most preferably a methoxy group, a is an integer of 0, 1 or 2, 1 is most preferred.)
The effect of significantly improving the weather resistance is contained when the (meth) acrylic polymer portion is inherently good in weather resistance and when the surface of the cured product is exposed to sunlight for a long time. It is presumed that the polymerizable unsaturated group reacts or polymerizes with light to further improve the weather resistance by increasing the crosslinking of the cured product surface.
In the polymer (A), the position where the crosslinkable silyl group and the polymerizable unsaturated group are present may be at the end of the polymer main chain or at any position in the main chain. The number of crosslinkable silyl groups is preferably 0.1 or more on average in the molecule, more preferably 0.4 to 6, and particularly preferably 0.4 to 3. When the number of crosslinkable silyl groups is less than 0.1, the curing tends to be insufficient, which is not preferable.
The polymerizable unsaturated group may be any one that reacts or polymerizes with light such as sunlight, but the ethylenically unsaturated group mainly composed of the (meth) acrylic monomer. Those in which a polymerizable unsaturated group remains and is contained when a saturated compound is radically polymerized or copolymerized are preferred. The content of polymerizable unsaturated groups in the polymer (A) is shown as the total degree of unsaturation, and the total degree of unsaturation is a value measured by a quantitative method by the Wijs method (Wiis method) described later of 0.01 meq. / G or more, particularly 0.01 to 2 meq / g is most preferable. The polymer (A) has a polystyrene-equivalent number average molecular weight of 1,000 to 50,000, more preferably 1,000 to 30,000, particularly 1,000 to 10,000, as determined by gel permeation chromatography. The viscosity at 25 ° C. is preferably 100,000 mPa · s or less, particularly preferably 50,000 mPa · s or less. When the total degree of unsaturation is less than 0.01 meq / g, the effect of improving the weather resistance becomes insufficient, and the number average molecular weight exceeds 50,000, and the viscosity at 25 ° C. exceeds 100,000 mPa · s. The workability of the composition is deteriorated. Further, the polymer (A) is characterized by a small amount of polymerizable unsaturated groups and a high molecular weight, so that a Michael addition reaction by a secondary amine is difficult to occur. For example, hindered secondary amine-based antioxidant is prevented. Even if an agent is used, it is mentioned that the storage stability of the obtained curable composition is favorable.

A method of introducing a crosslinkable silyl group into a polymer main chain obtained by radical polymerization or copolymerization of the ethylenically unsaturated compound containing the (meth) acrylic monomer as a main component may be a known method. The method like this is mentioned.
(1) A method of copolymerizing a compound having a polymerizable unsaturated group and a crosslinkable silyl group (for example, CH ₂ ═CHSi (OCH ₃ ) ₃ ) and a (meth) acrylic acid alkyl ester monomer.
(2) A compound having a polymerizable unsaturated group and a functional group (for example, hydroxyethyl (meth) acrylate) is added to a (meth) acrylic acid alkyl ester monomer for copolymerization, and then the function of the copolymer to be formed A method of reacting a group, a group that reacts with this functional group, and a compound having a crosslinkable silyl group (for example, a compound having an isocyanate group and —Si (OCH ₃ ) ₃ group).
Among these methods, a hydroxyl group and a polymerizable unsaturated group-containing (meth) acrylic polymer (a), a crosslinkable silyl group-containing isocyanate compound (b), and optionally an organic monoisocyanate are sequentially or simultaneously. A method of reacting is preferable.

More specifically, the hydroxyl group and polymerizable unsaturated group-containing (meth) acrylic polymer (a) and the crosslinkable silyl group-containing isocyanate compound (b) are mixed at an isocyanate group / hydroxyl group equivalent ratio of 0.1 to 0.1. It can be suitably produced by reacting in the range of 1.5 / 1.0, and further 0.4 to 1.0 / 1.0. Further, when the hydroxyl group and polymerizable unsaturated group-containing (meth) acrylic polymer (a), the crosslinkable silyl group-containing isocyanate compound (b) and the organic monoisocyanate are reacted, preferably, the hydroxyl group and polymerization are first performed. The unsaturated group-containing (meth) acrylic polymer (a) and the crosslinkable silyl group-containing isocyanate compound (b) have an isocyanate group / hydroxyl group equivalent ratio of 0.1 to 0.99 / 1.0, By reacting in the range of 0.4 to 0.8 / 1.0, a crosslinkable silyl group, a polymerizable unsaturated group, and a hydroxyl group-containing (meth) acrylic polymer are synthesized, and then an organic monoisocyanate is added thereto. The crosslinkable silyl group and polymerizability are obtained by reacting in the range where the equivalent ratio of isocyanate group / hydroxyl group of the total raw material is 0.2 to 1.5 / 1.0, and further 0.5 to 1.0 / 1.0. Contains unsaturated groups (meta Synthesizing an acrylic polymer (A). In this case, it is also possible to react the crosslinkable silyl group-containing isocyanate compound (b) after reacting the organic monoisocyanate first.
When the isocyanate group / hydroxyl group equivalent ratio of the crosslinkable silyl group-containing isocyanate compound (b) is less than 0.1 / 1.0, the content of the crosslinkable silyl group in the polymer (A) becomes too small. If the ratio exceeds .5 / 1.0, excess isocyanate groups react with moisture during the curing to generate carbon dioxide and cause foaming, or the cost increases.
In addition, it is more preferable to use organic monoisocyanate in terms of easy adjustment of physical properties and improvement of water resistance, and further, hydroxyl group and polymerizable unsaturated group-containing (meth) acrylic polymer (a) and crosslinkable silyl group. It is preferable to sequentially react the containing isocyanate compound (b) and the organic monoisocyanate because the reaction can be easily controlled.
In these reactions, metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese and iron with organic acids such as octyl acid and naphthenic acid, dibutyltin dilaurate, dioctyltin dilaurate, etc. Known urethanization catalysts such as organic metal and organic acid salts, organic amines such as triethylenediamine, triethylamine, and tri-n-butylamine and salts thereof can be used, and among these, dibutyltin dilaurate is preferred.
Further, a known organic solvent can also be used.

  As the hydroxyl group and polymerizable unsaturated group-containing (meth) acrylic polymer (a) in the present invention, specifically, an ethylenically unsaturated compound containing a hydroxyl group-containing (meth) acrylic monomer is radically polymerized. Alternatively, a high molecular weight polymer obtained by copolymerization and having photoreactivity can be mentioned. More specifically, radical (co) polymerization reaction or high-temperature continuous radical (co) polymerization of the monomers described below in the presence or absence of a radical polymerization initiator at 50 to 300 ° C. and further at 80 to 280 ° C. The number average molecular weight in terms of polystyrene by gel permeation chromatography obtained by the reaction is 500 to 50,000, more preferably 1,000 to 30,000, particularly 1,000 to 10,000, and Tg is 0 ° C. or lower. A (meth) acrylic polymer having a viscosity at −80 to −20 ° C. and 25 ° C. of 100,000 mPa · s or less, particularly 50,000 mPa · s or less, and containing a polymerizable unsaturated group in the molecule. Preferably, the total degree of unsaturation of the (meth) acrylic polymer is 0.01 meq / g or more, especially 0, as measured by a quantitative method according to the Wijs method (Wiis method) described later. It is the most preferred of 01~2meq / g. When the number average molecular weight is 50,000, the Tg is 0 ° C., and the viscosity exceeds 100,000 mPa · s, the viscosity of the resulting curable composition is increased, the workability is deteriorated, and the total unsaturation is 0.01 meq. If it is less than / g, the weather resistance imparting effect is reduced, and if the number average molecular weight is less than 500, the cured product becomes brittle without rubber elasticity, which is not preferable. The hydroxyl group and polymerizable unsaturated group-containing (meth) acrylic polymer (a) may further have an active hydrogen group such as a carboxyl group or may not have an isocyanate group, It does not contain a crosslinkable silyl group. Note that the photoreactive property of the hydroxyl group and polymerizable unsaturated group-containing (meth) acrylic polymer (a) is such that a small amount of polymerizable unsaturated groups ( This is presumably because it contains (residual) ethylenically unsaturated groups.

As an ethylenically unsaturated compound containing a hydroxyl group-containing (meth) acrylic monomer, specifically, a compound comprising a hydroxyl group-containing (meth) acrylic monomer, or a hydroxyl group-containing (meth) acrylic monomer And an ethylenically unsaturated monomer other than the hydroxyl group-containing (meth) acrylic monomer. From those polymerized using a hydroxyl group-containing (meth) acrylic monomer, an ethylenically unsaturated monomer other than a hydroxyl group-containing (meth) acrylic monomer and a hydroxyl group-containing (meth) acrylic monomer is used. A copolymer obtained by using a monomer is preferable because a hydroxyl group and a polymerizable unsaturated group-containing (meth) acrylic polymer (a) having a low viscosity can be obtained.
The hydroxyl group-containing (meth) acrylic monomer is preferably an alcoholic hydroxyl group-containing (meth) acrylic monomer. Specifically, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dipentaerythritol penta (meth) acrylate, ditrimethylol Hydroxyl group content such as mono (meth) acrylates of polyhydric alcohols such as propane tri (meth) acrylate and polypropylene glycol mono (meth) acrylate or poly (meth) acrylates having residual hydroxyl groups Meth) acrylic acid ester monomer can be mentioned, such as adducts of cyclohexene oxide in addition to these (meth) with epoxides, such as an adduct of acrylic acid and (meth) acrylic acid. These can be used alone or in combination of two or more. Of these, the resulting polymer has a low viscosity and a high weather resistance-improving effect, and has a low molecular weight of less than 500 and a (meth) acryloyl group containing one alcoholic hydroxyl group in the molecule. Ester monomers are preferred, and hydroxyethyl (meth) acrylate is more preferred.
As an ethylenically unsaturated monomer other than a hydroxyl group-containing (meth) acrylic monomer, a (meth) acrylic acid ester monomer that does not contain a hydroxyl group, and other than these that can be used as necessary Examples of the (meth) acrylic acid ester-based monomer that does not contain a hydroxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and the like. Butyl (meth) acrylate, Isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, behenyl (meth) acrylate , Benzyl (meth) acrylate, glycidyl (meth) acrylate, ethoxylated phenol (meth) acrylate, ethoxylated polymer Cumylphenol (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propoxylated nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, Mono (meta) such as tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxy (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, tridecyl (meth) acrylate ) Acrylic acid ester monomer, ethoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol A (Meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, caprolactone di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate Poly (meth) acrylic acid such as acrylated, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated glycerol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate Examples include ester monomers. These can be used alone or in combination of two or more. Among these, low molecular weight mono (meth) acrylate ester monomers not containing a hydroxyl group with a molecular weight of less than 500 are preferable in the same manner as described above, and are methyl (meth) acrylate, ethyl (meth) acrylate, More preferred are propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
Other ethylenically unsaturated monomers that can be used as necessary include ethylene, propylene, isobutylene, chloroprene, vinyl chloride, vinylidene chloride, (meth) acrylic acid, vinyl acetate, acrylonitrile, styrene, Examples include chlorostyrene, 2-methylstyrene, divinylbenzene, (meth) acrylamide, N-vinyl-2-pyrrolidone, and (meth) acrylic acid dimer. These can be used alone or in combination of two or more. Of these, (meth) acrylic acid and styrene are preferable in the same manner as described above.

  The crosslinkable silyl group-containing isocyanate compound (b) may contain at least one isocyanate group and one or more crosslinkable silyl groups in the molecule, but it is easy to control the reaction and rubber after curing. From the viewpoint of good elasticity, a compound containing one isocyanate group and one crosslinkable silyl group in the molecule is preferable. The crosslinkable silyl group is preferably the one represented by the general formula (1) from the viewpoint of easy production and crosslinking.

  Specific examples of the crosslinkable silyl group-containing isocyanate compound (b) include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, and 3-isocyanatepropylmethyldimethoxy. Examples include silane, 3-isocyanatopropylisopropoxysilane, isocyanate trimethoxysilane, and diisocyanate dimethoxysilane. These can be used alone or in combination of two or more. Of these, 3-isocyanatopropyltrimethoxysilane is preferred.

  The organic monoisocyanate is used for the purpose of adjusting the number of functional groups of the crosslinkable silyl group for the purpose of adjusting physical properties and the purpose of improving the water resistance, and it is sufficient to contain one isocyanate group in the molecule. It does not contain a silyl group. That is, the organic group other than the isocyanate group of the organic monoisocyanate does not contain a moisture-curable functional group such as moisture, and is preferably a hydrophobic organic group. Specifically, aliphatic monoisocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate, n-tetradecyl monoisocyanate, n-hexadecyl monoisocyanate, octadecyl monoisocyanate, n-chloroethyl monoisocyanate, chlorophenyl monoisocyanate Isocyanate, 3,5-dichlorophenyl monoisocyanate, p-fluorophenyl monoisocyanate, 2,4-difluorophenyl monoisocyanate, o-trifluoromethylphenyl monoisocyanate, p-nitrophenyl monoisocyanate, p-isopropylphenyl monoisocyanate, 2 , 6-Diisopropyl monoisocyanate, p-toluenesulfonyl monoisocyanate, p-benzyloxyphenyl monoisocyanate Aromatic monoisocyanate such as, other 2-methacryloyloxyethyl isocyanate. These can be used alone or in admixture of two or more. Of these, aliphatic monoisocyanates are preferred, and octadecyl monoisocyanate is more preferred.

In the present invention, in addition to the crosslinkable silyl group and the polymerizable unsaturated group-containing (meth) acrylic polymer (A), the other crosslinkable silyl group-containing organic polymer (B) is used as a curing component. Can be used in combination. The crosslinkable silyl group-containing organic polymer (B) is generally called a silicone resin and a modified silicone resin, and contains a crosslinkable silyl group and a polymerizable unsaturated group-containing (meth) acrylic polymer (A ), A resin containing a crosslinkable silyl group in the molecule that forms a rubber-like cured product by reacting with moisture (water) to form a siloxane bond. Of these, modified silicone resins are preferred in that they can be produced at a relatively low cost and the rubber elastic properties after curing can be adjusted over a wide range.
The silicone resin is a resin having a main chain of organopolysiloxane and a crosslinkable silyl group in the molecule.
As the modified silicone resin, for example, JP-A-52-73998, JP-A-55-9669, JP-A-59-122541, JP-A-60-6747, JP-A-61-233043 JP-A-63-112642, JP-A-3-79627, JP-A-4-283259, JP-A-5-70531, JP-A-5-287186, JP-A-11-80571. Examples disclosed in Japanese Patent Laid-Open Nos. 11-116763 and 11-130931 can be given. Specifically, aliphatic hydrocarbon hydrocarbon polymer such as polyoxyalkylene polymer, polyisoprene, polyisobutylene, polybutanediene, etc., containing a crosslinkable silyl group in the molecule, polyester polymer heavy Examples thereof include a polymer, a polysulfide polymer, a copolymer thereof, and a mixture thereof.
The main chain of the modified silicone resin is preferably a polyoxyalkylene polymer, more preferably a polyoxypropylene polymer, from the viewpoint of physical properties such as tensile adhesion after curing and modulus.
The crosslinkable silyl group is preferably contained in the molecule in an amount of 0.1 or more, particularly 1 to 5 in terms of the curability of the composition and the physical properties after curing.
Further, the crosslinkable silyl group is preferably the one represented by the general formula (1) which is easily crosslinked and easily produced.

Introduction of the crosslinkable silyl group into the main chain can be performed, for example, by the following known method.
(1) A polyoxyalkylene polymer having a functional group such as a hydroxyl group at the terminal is reacted with an organic compound (for example, allyl isocyanate) having an active group and an unsaturated group that are reactive with the functional group. Subsequently, hydrosilylation is performed by allowing hydrosilane having a hydrolyzable group to act on the obtained reaction product.
(2) A polyoxyalkylene-based polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group at the terminal is reacted with a compound having a functional group showing reactivity to the functional group and a crosslinkable silyl group. Let
Examples of the compound having a reactive functional group and a crosslinkable silyl group include amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, and the crosslinkable silyl group-containing isocyanate compound.
In the present invention, the number average molecular weight of the silicone resin or the modified silicone resin is 1,000 or more, particularly those having a narrow molecular weight distribution at 6,000 to 30,000, which are easy to handle because the viscosity of the curable composition is low, It is suitable because it has excellent physical properties such as strength, elongation and modulus after curing.

In the present invention, the crosslinkable silyl group-containing polyoxyalkylene polymer preferable as a curing component that can be used in combination is preferably a polyoxyalkylene polyol and a crosslinkable silyl group-containing isocyanate compound. In some cases, the organic isocyanate can be reacted successively or simultaneously.
When the polyoxyalkylene polyol and the crosslinkable silyl group-containing isocyanate compound are reacted, the equivalent ratio of isocyanate group / hydroxyl group is 0.1 to 1.5 / 1.0, more preferably 0.5 to 1.0 / 1. It is preferable to carry out the reaction within the range of 0.0. Further, when the polyoxyalkylene polyol, the crosslinkable silyl group-containing isocyanate compound and the organic isocyanate are reacted sequentially or simultaneously, the polyoxyalkylene polyol and the crosslinkable silyl group-containing isocyanate compound have an isocyanate group / hydroxyl group equivalent ratio. It is preferable to react in the range of 0.1 to 0.99 / 1.0, more preferably 0.5 to 0.95 / 1.0, and the resulting crosslinkable silyl group and hydroxyl group-containing polyoxyalkylene polymer And the organic isocyanate are reacted in a range where the equivalent ratio of isocyanate group / hydroxyl group of the total raw material is 0.2 to 1.5 / 1.0, more preferably 0.6 to 1.0 / 1.0. preferable.
In this reaction, the known urethanization catalyst mentioned in the synthesis of the crosslinkable silyl group and the polymerizable unsaturated group-containing (meth) acrylic polymer (A) can be used. An organic solvent can also be used.

Examples of the polyoxyalkylene polyol include those obtained by ring-opening addition polymerization of alkylene oxide and those obtained by ring-opening addition polymerization of alkylene oxide in an initiator.
Initiators include low-molecular-weight compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, and shoelacese. Examples include alcohols, polyhydric phenols such as bisphenol A, low molecular polyamines such as ethylenediamine, and low molecular amino alcohols such as diethanolamine.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran.
That is, the polyoxyalkylene polyol specifically includes, for example, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, random copolymer or block copolymer poly (oxyethylene) -poly (oxypropylene) -glycol. , Random copolymer or block copolymer poly (oxyethylene) -poly (oxybutylene) -glycol and the like, and various polyols such as toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. A known polyisocyanate is allowed to react with an isocyanate group in an excess of hydroxyl groups so that the molecular terminal is a hydroxyl group. These can be used alone or in combination of two or more. Of these, polyoxypropylene glycol is particularly preferred.
The polyoxyalkylene polyol preferably has a number average molecular weight of 1,000 to 30,000, more preferably 6,000 to 30,000, from the viewpoint of high elongation of the cured product. The number is preferably from 1 to 8, particularly preferably from 2 to 4, and more preferably a narrow molecular weight distribution having a total unsaturation value of 0.07 meq / g or less, particularly 0.04 meq / g or less.

  As said crosslinkable silyl group containing isocyanate compound, said crosslinkable silyl group containing isocyanate compound (b) used in the synthesis | combination of a crosslinkable silyl group and a polymerizable unsaturated group containing (meth) acrylic-type polymer (A). The same thing is mentioned.

As said organic isocyanate, organic monoisocyanate and organic polyisocyanate are mentioned, Among these, organic monoisocyanate is preferable.
Examples of the organic monoisocyanate are the same as those used in the synthesis of the crosslinkable silyl group and polymerizable unsaturated group-containing (meth) acrylic polymer (A).
The organic polyisocyanate may contain two or more isocyanate groups in the molecule, but does not contain a crosslinkable silyl group. Specifically, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,2-phenylene diisocyanate 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, chlorophenylene-2,4-diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3 ' -Aromatic diisocyanates such as dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, 1,6-hexamethylene diiso Anate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, decamethylene diisocyanate, lysine diisocyanate, etc. Aliphatic diisocyanates such as aliphatic diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogen Examples include alicyclic diisocyanates such as added diphenylmethane diisocyanate. Furthermore, organic polyisocyanates such as polymethylene polyphenyl polyisocyanate and crude toluene diisocyanate can also be used.
In addition, modified isocyanates containing one or more uretdione bonds, isocyanurate bonds, allophanate bonds, burette bonds, uretonimine bonds, carbodiimide bonds, urethane bonds, urea bonds, and the like obtained by modifying these organic isocyanates can also be used. These can be used alone or in admixture of two or more.
In the present invention, for example, a polyoxyalkylene polymer in which a crosslinkable silyl group is introduced using a urethane bond and a polyoxyalkylene polymer in which a crosslinkable silyl group is introduced by another method are mixed singly or in combination. A polyoxyalkylene polymer introduced with a crosslinkable silyl group by various methods can be used alone or in combination.

  In the present invention, the blending ratio of the crosslinkable silyl group-containing organic polymer (B) / crosslinkable silyl group and polymerizable unsaturated group-containing (meth) acrylic polymer (A) is 0 part by weight / 100 parts by weight or more. It is preferably 99 parts by weight / 1 part by weight, and more preferably 20 parts by weight / 80 parts by weight to 80 parts by weight / 20 parts by weight.

Next, the additive in the curable composition of this invention is demonstrated.
Examples of the additive in the present invention include a curing catalyst, a weather resistance stabilizer, a filler, a plasticizer, an adhesiveness imparting agent, a thixotropic imparting agent, a storage stability improving agent (dehydrating agent), a colorant, and a designability imparting agent. Can be mentioned.

The curing catalyst is a catalyst for accelerating the curing of a polymer containing a crosslinkable silyl group, and specifically includes organometallic compounds, amines, etc., for example, tin octylate, tin naphthenate, etc. Dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, dibutyltin oxide, dibutyltin bis (triethoxysilicate), Tetravalent organic tin compound such as a reaction product of dibutyltin oxide and phthalate ester, dibutyltin bis (acetylacetonate), tin-based chelate compound EXCESTAR C-501 manufactured by Asahi Glass Co., zirconium tetrakis (acetylacetonate), Titanium tetrakis (A Cetylacetonate), aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetone nickel, acetylacetone zinc, acetylacetone manganese Compounds, organic acid lead salts such as lead octylate, titanates such as tetra-n-butyl titanate and tetrapropyl titanate, organic bismuth compounds such as bismuth octylate and bismuth versatate, and first such as butylamine and octylamine Secondary amines such as secondary amines, dibutylamine, dioctylamine, monoethanolamine, diethanolamine, triethanolamine Alkanolamines such as, primary amines such as diethylenetriamine and triethylenetetramine, secondary amines, tertiary amines such as triethylamine, tributylamine, triethylenediamine and N-ethylmorpholine, or these amines Examples thereof include salts such as carboxylic acids, inorganic acidic compounds such as kaolin clay and hydrochloric acid, organic phosphoric acid acidic compounds such as ethyl acid phosphate and 2-ethylhexyl acid phosphate, and salts of these with amines. Of these, organotin compounds and metal chelate compounds are preferred because of their high reaction rate and relatively low toxicity and volatility, and tin-based chelate compounds are more preferred, with dibutyltin bis (acetylacetonate) being the most preferred. preferable.
The curing catalyst is from 0 to 10 parts by weight with respect to 100 parts by weight of the total of the polymers (A) and (B) containing a crosslinkable silyl group as a curing component from the viewpoints of curing speed and physical properties of the cured product. In particular, it is preferable to blend 0.01 to 2 parts by weight.

  The weathering stabilizer is used to prevent oxidation, photodegradation and thermal degradation after curing of the polymer containing a crosslinkable silyl group, and to further improve not only the weather resistance but also the heat resistance. Specific examples of the weather stabilizer include an antioxidant and an ultraviolet absorber.

Specific examples of the antioxidant include hindered amine-based and hindered phenol-based antioxidants. Examples of the hindered amine-based antioxidant include bis (1,2,2,6,6-pentamethyl). -4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate Methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine and the like. Moreover, low molecular weight less than 1,000, such as LA-52, LA-57, LA-62, LA-67, LA-77, LA-82, LA-87 of the brand name ADK STAB series manufactured by Asahi Denka Kogyo Co., Ltd. High molecular weight hindered amine antioxidants with a molecular weight of 1,000 or more, such as 119FL, 2020FDL, 944FD, 944LD, etc. of molecular weight hindered amine antioxidants, also LA-63P, LA-68LD or Ciba Specialty Chemicals brand names CHIMASORB series Examples include agents.
Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert). -Butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], benzenepropanoic acid 3 , 5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and the like.

  Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, and 2- (4,6-diphenyl- Triazine-based UV absorbers such as 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, benzophenone-based UV absorbers such as octabenzone, 2,4-di-tert-butylphenyl Examples include benzoate-based ultraviolet absorbers such as -3,5-di-tert-butyl-4-hydroxybenzoate.

  The weathering stabilizer is 0.01 to 30 parts by weight, particularly 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the polymers (A) and (B) containing a crosslinkable silyl group as a curing component. It is preferable to mix.

  Fillers, plasticizers, adhesion-imparting agents, thixotropic agents, storage stability improvers (dehydrating agents), colorants, design-improving agents, etc. are reinforced, increased, reduced viscosity, improved adhesiveness, thixotropic, respectively. It can be used for improving design, improving storage stability, coloring, matting of the surface of the cured product and imparting unevenness (giving a feeling of roughness).

  Examples of fillers include mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, anhydrous silicic acid, quartz fine powder, aluminum powder, zinc powder, and synthetic silica such as precipitated silica, heavy Inorganic fillers such as calcium carbonate, light calcium carbonate, magnesium carbonate, alumina, calcium oxide, magnesium oxide, inorganic fillers such as asbestos, glass fibers, carbon fibers, etc., or their surface Fillers treated with organic substances such as fatty acids, wood flour, walnut flour, rice husk flour, pulp powder, cotton chips, rubber powder, polyamide resin, polyester resin, polyurethane resin, silicone resin, vinyl chloride resin, vinyl acetate resin, Polyolefin resin such as polyethylene and polypropylene, acrylic resin In addition to organic fillers such as epoxy resin, phenolic resin, urea resin, melamine resin and other thermoplastic resins or thermosetting resin powder, flame retardant fillers such as magnesium hydroxide and aluminum hydroxide And a particle size of 0.01 to 1,000 μm is preferable.

  Specific examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, and butyl benzyl phthalate, dicarboxylic acid adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate. Low molecular weight plasticizer having a molecular weight of less than 500, such as esters, alcohol esters such as pentaerythritol ester, phosphate esters such as trioctyl phosphate, tricresyl phosphate, halogenated aliphatic compounds such as chlorinated paraffin, polyether polyol Alternatively, polyethers obtained by etherification or esterification thereof, in particular, polyether polyols obtained by addition polymerization of ethylene oxide or propylene oxide to saccharide polyhydric alcohols such as sucrose, or etherification or esterification thereof, etc. Examples include saccharide-based polyoxyalkylenes, polybutadiene, butadiene-acrylonitrile copolymers, polychloroprene, polyisoprene, and high molecular weight plasticizers having a molecular weight of 500 or more such as olefin polymers such as hydrogenated polybutene. To prevent surface contamination due to adhesion of the surface by sticking to the surface of the cured product or the surface of the coating of the paint overcoated on the cured product surface (bleeding) It is preferable not to use the agent or to suppress the usage amount as much as possible even if it is used. For the same reason, a high molecular weight plasticizer having a molecular weight of 500 or more is preferable.

Examples of the adhesion-imparting agent include coupling agents, epoxy resins, phenol resins, alkyd resins, and organic polyisocyanates similar to the above organic polyisocyanates. Examples of the coupling agent include various coupling agents such as silane-based, aluminum-based, zircoaluminate-based, and titanium-based compounds and / or partial hydrolysis condensates thereof. Of these, a silane coupling agent and / or a partially hydrolyzed condensate thereof is preferred because of its excellent adhesiveness.
As silane coupling agents, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, ethyltrimethoxysilane, diethyldiethoxysilane, n-butyltrimethoxysilane, n-hexyltriethoxysilane , N-octyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane and other hydrocarbon group-bonded alkoxysilanes, dimethyldiisopropenoxysilane, methyltriisopropenoxysilane and other hydrocarbon group-bonded Isopropenoxysilanes, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmeth Sisilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-glycidoxypropylmethyl Diisopropenoxysilane, 3-glycidoxypropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-acryloxypropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and other functional groups such as alkoxysilanes and isopropenoxysilanes having a molecular weight of 500 or less, preferably 400 or less. Compounds having a molecular weight 200 to 3,000 are exemplified in compound and / or one or more partially hydrolyzed condensate of the silane coupling agent.

  Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica, asbestos powder, and fatty acid-treated calcium carbonate, and organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide.

  Examples of the storage stability improver include low molecular crosslinkable silyl group-containing compounds such as vinyltrimethoxysilane, calcium oxide, and p-toluenesulfonyl isocyanate, which react with moisture present in the composition.

  Examples of the colorant include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.

Designability-imparting agents can be used to aid in delustering the surface of the cured product by blending it into the curable composition and the sealing material composition, or to erase the surface luster and impart irregularities to simulate natural rough rocks. For example, various waxes such as beeswax, carnauba wax, montan wax, paraffin wax, etc. , Higher fatty acid amides such as stearic acid amide, compounds that react with oxygen in the air typified by drying oils such as tung oil and linseed oil, primary and / or secondary amines having a melting point of 35 ° C. or higher, water And a compound that reacts with aldehyde to produce a primary and / or secondary amine having a melting point of 35 ° C. or higher. Primary and / or secondary amines having a melting point of 35 ° C. or higher include higher aliphatic primary monoamines such as tetradecylamine, pentadecylamine, stearylamine, 1,8-diaminooctane, 1,9- Higher aliphatic primary diamines such as diaminononane and 1,10-diaminodecane, higher aliphatic secondary monoamines such as dilaurylamine, distearylamine and methyllaurylamine, N-laurylpropylenediamine, N-stearylpropylenediamine And higher aliphatic primary and secondary mixed polyamines. Examples of the compound that reacts with water to produce a primary and / or secondary amine having a melting point of 35 ° C. or higher are the compounds mentioned as the primary and / or secondary amine having a melting point of 35 ° C. or higher. And ketones such as methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, diisopropyl ketone, diisobutyl ketone, 4-methyl-2 pentanone, butyraldehyde, Examples thereof include ketimine compounds, aldimine compounds, enamine compounds obtained by dehydration reaction with carbonyl compounds such as aldehydes such as isobutyraldehyde and hexyl aldehyde. Of these, a compound that reacts with oxygen in the air and a primary and / or secondary amine having a melting point of 35 ° C. or higher are preferable because of a good matting effect.
Examples of the material that removes the gloss of the surface and imparts irregularities include granular materials and balloons, etc. The granular materials are the same as those mentioned as the filler, and large particles having a particle size of 50 μm or more are mentioned. It is done.
The balloon is a hollow substance, and the shape of the balloon is not only spherical, but also various shapes such as a cubic shape, a rectangular shape, and a confetti shape, and the balloon is slightly removed to the extent that the unevenness imparting effect on the curable composition and the sealing material composition is not lost. Although what was destroyed is also mentioned, spherical shape is preferable from the good workability | operativity of a curable composition and a sealing material composition. Specifically, for example, inorganic balloons such as glass balloons, shirasu balloons, silica balloons, ceramic balloons, organic balloons such as phenol resin balloons, urea resin balloons, polystyrene balloons, polyethylene balloons, saran balloons, or inorganic compounds and organic balloons Examples thereof include a composite balloon in which a system compound is mixed or laminated.
Also, those coated or surface-treated with these balloons can be used. For example, inorganic balloons surface-treated with the silane coupling agent, etc., organic balloons with calcium carbonate, talc, titanium oxide, etc. Examples of coatings are also included.
Of these, from the viewpoint of the effect of imparting designability, granular materials and / or balloons are preferable, and granular inorganic fillers and / or inorganic balloons are more preferable, especially coarse heavy calcium carbonate and / or ceramics. A balloon is preferred.
The particle size of the granular material and / or balloon is preferably 50 μm or more, and more preferably 100 to 1,000 μm, from the viewpoint of the effect of providing designability.

  The total amount of filler, plasticizer, adhesiveness imparting agent, thixotropic imparting agent, storage stability improver (dehydrating agent), colorant and designability imparting agent contains a crosslinkable silyl group as a curing component. 0 to 500 parts by weight, particularly 10 to 300 parts by weight is preferable with respect to 100 parts by weight of the total of the polymers (A) and (B).

  In the present invention, each additive component can be used alone or in combination of two or more.

  In the present invention, a curable composition having sufficiently good workability can be obtained without using an organic solvent, but it can also be used. However, even when used, it is preferable to suppress the amount of the organic solvent used as much as possible in order to prevent toxicity to workers and prevent environmental pollution, and the amount used is preferably less than 10% by mass in the curable composition. It is preferably less than 5% by mass, more preferably less than 1% by mass, and most preferably 0% by mass. Examples of the organic solvent include conventionally known organic solvents such as aliphatic solvents such as n-hexane, alicyclic solvents such as cyclohexane, aromatic solvents such as toluene and xylene, and the like. Anything that does not react to the above can be used.

Although the curable composition of the present invention can be used as a one-pack type or a two-pack type depending on the application, there is no trouble of mixing the main agent and the curing agent, and there are also problems such as poor curing due to poor mixing. Since it is excellent in workability, a one-component moisture curable composition is preferred.
Further, the container for storing the curable composition of the present invention is not particularly limited. For example, various containers such as a drum can, a metal or synthetic resin pail can or a bag-like container, a paper or synthetic resin cartridge-like container may be used. Can be mentioned. When used as a one-pack type moisture curable composition, it is preferably stored in a state of sealing and blocking moisture in order to maintain the storage stability of the contents.
The curable composition can be applied or filled by brush, spatula, roll coater, spray gun, etc., or packed in a bag-like or cartridge-like container attached to an extrusion gun, manually, electrically or pneumatically. Various methods such as extrusion filling may be mentioned, and the method may be appropriately selected depending on the application.

Hereinafter, the present invention will be described in more detail with reference to examples.
Here, although the one-component moisture-curing sealing material composition has been shown as an example of the curable composition, the present invention is not limited to this.

[Synthesis of acrylic copolymer containing hydroxyl group and polymerizable unsaturated group]
Synthesis example 1
The temperature of a 6 L capacity pressurized stirred tank reactor equipped with a heating and cooling device was maintained at 200 ° C. Separately, in the raw material tank, from a blending ratio of 39.0 g of butyl acrylate, 57.0 g of 2-ethylhexyl acrylate, 4.0 g of hydroxyethyl acrylate, and 0.1 g of ditertiary butyl peroxide as a radical polymerization initiator. A monomer mixture was prepared.
The monomer mixture was continuously fed from the raw material tank into the reactor at a constant feed rate (22 g / min, residence time: 12 minutes), while maintaining the reactor pressure constant, A reaction product corresponding to the supply amount was continuously withdrawn from the outlet. Immediately after the start of the reaction, once the reaction temperature decreased, an increase in temperature due to the heat of polymerization was observed, but the reaction temperature was maintained at 200 to 205 ° C. by controlling the temperature by cooling or heating.
The continuous supply of the monomer mixture was started, and 40 minutes after the temperature became stable, the reaction liquid collection start point was set. As a result of continuing the reaction for 60 minutes, 1320 g of the monomer mixture liquid was supplied. The reaction solution was collected. Thereafter, the reactor was introduced into a thin film evaporator to separate volatile components such as unreacted monomers. As a result of measurement by gas chromatography, no unreacted monomer was present in the concentrate.
The resulting acrylic copolymer containing hydroxyl groups and polymerizable unsaturated groups has a polystyrene-reduced number average molecular weight of 5,000, a viscosity of 12,000 mPa · s / 25 ° C., and a hydroxyl value of 21 by gel permeation chromatography. (MgKOH / g), glass transition temperature (Tg) by differential scanning calorimetry (DSC) is −50 to −55 ° C., and the total unsaturation degree by Wijs method (Wiis method) is 0.216 meq / g. It was a liquid. This hydroxyl- and polymerizable unsaturated group-containing acrylic copolymer is referred to as a1.
This was coated on a slate plate and irradiated with light for 100 hours using a metal weather meter manufactured by Daipura Wintes Co., and then gelled and solidified to confirm that it had photoreactivity.

(Synthesis of crosslinkable silyl group and polymerizable unsaturated group-containing acrylic copolymer)
Synthesis example 2
A hydroxyl group and polymerizable unsaturated group-containing acrylic copolymer a1 (number average) obtained in Synthesis Example 1 under a nitrogen gas stream in a heating / cooling reactor equipped with a stirrer, thermometer and nitrogen seal tube Charged 800 g (OH equivalent: 0.3) of molecular weight 5,000, hydroxyl value 21 mgKOH / g, Tg-50 to -55 ° C., total unsaturation 0.216 meq / g), and stirring with 3-isocyanatopropyltrimethoxy After adding 30 g of silane (Y-5187 manufactured by Nihon Unicar, molecular weight 205.4) (NCO equivalent: 0.15) (R value (NCO equivalent / OH equivalent) = 0.5) and 0.08 g of dibutyltin dilaurate The mixture was heated and stirred at 70 to 80 ° C. for 3 hours, and disappearance of the peak of the isocyanate group was confirmed by FTIR, and the reaction was terminated by cooling to room temperature.
The obtained trimethoxysilyl group and polymerizable unsaturated group-containing acrylic copolymer was translucent at room temperature with an isocyanate group content of 0.00 mass% and a viscosity of 15,000 mPa · s / 25 ° C. measured theoretically and by titration. It was a viscous liquid. This acrylic copolymer containing trimethoxysilyl group and polymerizable unsaturated group is referred to as A1.
The total degree of unsaturation calculated from the raw material of this copolymer A1 is 0.208 meq / g.

Synthesis example 3
In a reaction vessel similar to Synthesis Example 2, under a nitrogen stream, the hydroxyl group and polymerizable unsaturated group-containing acrylic copolymer a1 obtained in Synthesis Example 1 (number average molecular weight 5,000, hydroxyl value 21 mgKOH / g, total 734 g (OH equivalent: 0.27) of unsaturation degree 0.216 meq / g) was charged, and 27.5 g (NCO) of 3-isocyanatopropyltrimethoxysilane (Nihon Unicar Y-5187, molecular weight 205.4) with stirring. Equivalent: 0.134) (R value (NCO equivalent / OH equivalent) = 0.5) and 0.07 g of dibutyltin dilaurate were added, and the mixture was heated and stirred at 70-80 ° C. for 3 hours, and subjected to FTIR After confirming the disappearance of the peak of the isocyanate group, it was cooled to room temperature. Then, in this, octadecyl monoisocyanate (Mionate O manufactured by Hodogaya Chemical Co., Ltd., molecular weight 295) 39.5 g (NCO equivalent: 0.134) (R value (total NCO equivalent / OH equivalent) = 1.0) Was added, and the mixture was heated and stirred at 70 to 80 ° C. for 5 hours. The disappearance of the peak of the isocyanate group was confirmed by FTIR, and the reaction was terminated by cooling to room temperature.
The obtained trimethoxysilyl group and polymerizable unsaturated group-containing acrylic copolymer was translucent at room temperature with a theoretical, titration-measured isocyanate group content of 0.00 mass% and a viscosity of 17,000 mPa · s / 25 ° C. It was a viscous liquid. This acrylic copolymer containing trimethoxysilyl group and polymerizable unsaturated group is referred to as A2.
The total degree of unsaturation calculated from the raw material of this copolymer A2 is 0.198 meq / g.

(Synthesis of crosslinkable silyl group-containing polyoxypropylene polymer)
Synthesis example 4
A reaction vessel similar to Synthesis Example 2 was charged with 800 g (OH equivalent: 0.1) of polyoxypropylene glycol (number average molecular weight: 16,000, PML-4016 manufactured by Asahi Glass Co., Ltd.) under a nitrogen stream, while stirring. -19.5 g (NCO equivalent: 0.095) (R value (NCO equivalent / OH equivalent) = 0.95) and dibutyltin dilaurate (Yunicar Co., Ltd. Y-5187, molecular weight 205.4) After adding 0.01 g, the mixture was heated and stirred at 70 to 80 ° C. for 2 hours. The disappearance of the peak of the isocyanate group was confirmed by FTIR, and the reaction was terminated by cooling to room temperature.
The obtained trimethoxysilyl group-containing polyoxypropylene polymer is a semitransparent viscous liquid at ordinary temperature having a theoretical, titration-measured isocyanate group content of 0.00 mass% and a viscosity of 19,000 mPa · s / 25 ° C. Met. This trimethoxysilyl group-containing polyoxypropylene polymer is referred to as B1.

Example 1
In a kneading vessel equipped with a heating and cooling device and a nitrogen seal tube, 200 g of the trimethoxysilyl group-containing polymerizable unsaturated group-containing acrylic copolymer A1 obtained in Synthesis Example 2 and a fatty acid (surface) treated carbonic acid are obtained in a nitrogen stream. 200 g of calcium (N-2 manufactured by Maruo Calcium Co., Ltd.) was charged and mixed. Thereafter, dehydration under reduced pressure (20 to 70 hPa) is performed at 100 to 110 ° C. for 2 hours, and after cooling, a hindered phenol antioxidant: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate] (Irganox 1010 manufactured by Ciba Specialty Chemicals) and hindered amine antioxidant: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Sanol LS- manufactured by Sankyo) 770), 1 g of fatty acid amide (Fatty Acid Amide S manufactured by Kao Corporation), 5 g of vinyltrimethoxysilane (Silas Ace S210 manufactured by Chisso Corporation) and dibutyltin bis (acetylacetonate) (Neostan U-220 manufactured by Nitto Kasei Co. 0.2 g and N- (2-aminoethyl) -3-aminopropyl Chill dimethoxysilane (manufactured by Chisso Corporation Sila-Ace S310) a 2g charged, stirred and mixed, then filled in a vacuum degassing and container, sealed to prepare a sealant composition.

Example 2
In Example 1, instead of using 200 g of the trimethoxysilyl group and polymerizable unsaturated group-containing acrylic copolymer A1 obtained in Synthesis Example 2, the trimethoxysilyl group and polymerizable unsaturated group obtained in Synthesis Example 3 were used. A sealing material composition was prepared in the same manner except that 200 g of the group-containing acrylic copolymer A2 was used.

Example 3
In Example 1, instead of using 200 g of the trimethoxysilyl group and polymerizable unsaturated group-containing acrylic copolymer A1 obtained in Synthesis Example 2, the trimethoxysilyl group and polymerizable unsaturated group obtained in Synthesis Example 2 were used. A sealing material composition was prepared in the same manner except that 100 g of the group-containing acrylic copolymer A1 and 100 g of the trimethoxysilyl group-containing polyoxypropylene polymer B1 obtained in Synthesis Example 4 were used.

Example 4
In Example 2, instead of using 200 g of the trimethoxysilyl group and polymerizable unsaturated group-containing acrylic copolymer A2 obtained in Synthesis Example 3, the trimethoxysilyl group and polymerizable unsaturated group obtained in Synthesis Example 3 were used. A sealing material composition was prepared in the same manner except that 100 g of the group-containing acrylic copolymer A2 and 100 g of the crosslinkable silyl group-containing polyoxypropylene polymer (ES-S3630 manufactured by Asahi Glass Co., Ltd.) were used.

Comparative Example 1
Instead of using 200 g of the trimethoxysilyl group and polymerizable unsaturated group-containing acrylic copolymer A1 obtained in Synthesis Example 2 in Example 1, the trimethoxysilyl group-containing polyoxypropylene system obtained in Synthesis Example 4 was used. A sealing material composition was prepared in the same manner except that 200 g of the polymer B1 and 20 g of trimethylolpropane triacrylate were used.

Comparative Example 2
In Example 1, instead of using 200 g of the trimethoxysilyl group and polymerizable unsaturated group-containing acrylic copolymer A1 obtained in Synthesis Example 2, a crosslinkable silyl group-containing polyoxyalkylene polymer (manufactured by Asahi Glass Co., Ltd.) A sealing material composition was prepared in the same manner except that 200 g of ES-S3630) and 20 g of trimethylolpropane triacrylate were used.

[Quantification of total unsaturation by Wijs method (Wiis method)]
According to JIS K 0070 (1992), “6. Iodine number”, the total degree of unsaturation of the sample was quantified by the following method.
1) Preparation of reagents a) Iodine monochloride solution (Wiis solution)
Iodine trichloride (7.9 g) and iodine (8.9 g) were placed in separate flasks, and each was dissolved by adding glacial acetic acid. The two solutions were mixed, and the total amount was adjusted to 1 liter (l) with glacial acetic acid.
B) Sodium thiosulfate solution (0.1 mol / l)
A sodium thiosulfate solution (0.1 mol / l) was prepared according to JIS K 8001, 4.5 (21.2).
C) Starch solution (10 g / l)
1 g of starch was mixed with a small amount of water, added to 100 ml of boiling water, boiled for several minutes to make it transparent, and then cooled.
2) Operation (a) 2 g of a sample was taken in a 500 ml Erlenmeyer flask and weighed to an effective numerical value of 3 digits.
(B) 40 ml of chloroform was added to dissolve the sample.
(C) 20 ml of iodine monochloride solution was accurately taken with a whole pipette, added to an Erlenmeyer flask, and shaken and mixed.
(D) Sealed and left in a dark place at room temperature for 1 hour or more. Sometimes shaken.
(E) 2 g of potassium iodide was dissolved in 100 ml of deionized distilled water and added to the Erlenmeyer flask. The halogen adhering to the glass stopper thread was also poured into the container.
(F) Titrate with sodium thiosulfate solution (0.1 mol / l). When the solution turned pale yellow, several drops of starch solution were added and titrated until the blue color disappeared.
(G) In the blank test, (b) to (f) were performed without putting a sample.
3) Calculation The degree of unsaturation was calculated by the following equation.
Unsaturation = (A−B) × f / 20 × S
Where, A: titration of sodium thiosulfate solution (0.1 mol / mol) for blank test (m
l)
B: Sample titration of sodium thiosulfate (0.1 mol / l) (ml)
S: Mass of sample (g)
f: Factor of sodium thiosulfate solution (0.1 mol / l)

〔performance test〕
Using the sealing material compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the following tests were performed.
(1) Extrudability (immediately after production)
As a test for evaluating workability, an extrusion time was measured for a sealing material composition immediately after production according to “4.14 Extrusion Test with Cartridge for Testing” of JIS A1439: 1997 “Testing Method of Sealant for Building”. (Measurement temperature 23 ° C.).
Those having an extrusion time of 5 seconds or less were evaluated as ◯.
(2) Storage stability After the sealing material composition filled in the container is placed in a 50 ° C. incubator and stored for 10 days, the extrusion time is measured by the above-described method of extrusion test (measurement temperature is 23 ° C.). The storage stability was evaluated.
Those having an extrusion time of 5 seconds or less were evaluated as ◯, and those exceeding 5 seconds were evaluated as ×.
(3) Slump The slump (longitudinal) was measured in accordance with “4.1 slump test” in JIS A1439: 1997 “Testing method of sealing material for building” (measurement temperature: 23 ° C.).
(4) Tack-free Measured in accordance with “4.19 Tack-free test” in JIS A1439: 1997 “Testing method of building sealing material”.
A tack-free time of 5 hours or less was rated as “good”.
(5) Weather resistance The sealing material composition is formed into a sheet and cured for 14 days at 23 ° C. and 50% relative humidity to prepare a sheet having a thickness of 5 mm. Using a sunshine weatherometer according to JIS K6266: 1996 The state of the surface of the test piece after 1000 hours irradiation, 2000 hours irradiation, 3000 hours irradiation, and 4000 hours irradiation was visually observed.
Judgment criteria ○: No or few hair cracks on the test piece surface ×: There are many hair cracks on the test piece surface These results and the composition of the sealing material composition are shown together in Table 1.

  The curable composition of the present invention is particularly preferably used as a high-performance sealant for extending the life of exterior wall joints, civil joints, automobile joints, etc. by utilizing the above-mentioned characteristics. It can be suitably used as an adhesive or paint for automobile parts and the like. The curable composition of the present invention includes inorganic materials such as mortar and concrete, ceramic materials such as siding and tiles, various synthetic resin materials such as polyethylene and vinyl chloride, woody materials such as wood and plywood, steel plates and aluminum It can be applied to various materials such as metal materials such as plates.

Claims (8)

  A curable composition comprising a crosslinkable silyl group and a polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (A) as a curing component.   It contains a crosslinkable silyl group and a polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (A) and other crosslinkable silyl group-containing organic polymer (B) as a curing component. A curable composition.   The crosslinkable silyl group and polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (A) is a hydroxyl group and polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (a) and contains a crosslinkable silyl group. The curable composition of Claim 1 or 2 which is a reaction product with an isocyanate compound (b).   The hydroxyl group and polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (a) is a radical copolymerization of an ethylenically unsaturated compound containing a hydroxyl group-containing acrylic and / or methacrylic monomer at 50 to 300 ° C. An acrylic resin having a number average molecular weight of 500 to 50,000, a Tg of 0 ° C. or lower, a viscosity at 25 ° C. of 100,000 mPa · s or lower, and containing a hydroxyl group and a polymerizable unsaturated group in the molecule. 4. The curable composition according to claim 3, which is a methacrylic copolymer.   The total degree of unsaturation measured by the determination method by the Wijs method of the hydroxyl group and polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (a) is 0.01 meq / g or more. The curable composition as described.   The curable composition according to claim 2, wherein the crosslinkable silyl group-containing organic polymer (B) is a crosslinkable silyl group-containing polyoxyalkylene polymer.   Furthermore, the curable composition as described in any one of Claims 1-6 containing an additive.   A sealing material composition comprising a crosslinkable silyl group and a polymerizable unsaturated group-containing acrylic and / or methacrylic polymer (A) as a curing component.