JP6092552B2 - Curable composition and method for improving adhesion - Google Patents

Description

  In the present invention, the (meth) acrylic acid ester polymer (I) having at least one crosslinkable silyl group, and at least one crosslinkable silyl group having a specific (meth) acrylic acid ester in a weight ratio of 20 % Or more, and the solubility parameter (SP value) relates to a curable composition containing an organic polymer (II) that is 0.2 or more larger than the (meth) acrylate polymer (I). Moreover, it is related with the method of improving the adhesiveness by using together (meth) acrylic-ester type | system | group polymer (I) and organic polymer (II).

  An organic polymer containing at least one crosslinkable silyl group in the molecule is crosslinked at room temperature by the formation of a siloxane bond accompanied by a hydrolysis reaction of a reactive silicon group due to moisture or the like. It is known to have an interesting property of being obtained. Among these polymers having a crosslinkable silyl group, a vinyl polymer having at least one crosslinkable silyl group and a polyether polymer having at least one crosslinkable silyl group have been disclosed (patents). Documents 1 to 7) have already been industrially produced and are widely used in applications such as sealing materials, adhesives and paints.

  Sealing materials are generally used for the purpose of filling watertightness and airtightness by filling joints and gaps between various members. Therefore, because the long-term followability to the use site and the adhesion to the joint base material are extremely important, especially the working joints of buildings with large joint width fluctuations (headwood, glass, window frame, sash, Compositions used for sealing materials for curtain walls, various exterior panels), sealing materials for direct glazing, sealing materials for multi-layer glass, sealing materials for SSG method, etc. are required to have excellent adhesion and durability. .

  In general, for buildings with relatively little fluctuation in joint width, adhesion to joints etc. is ensured by including an adhesion-imparting agent in the sealing material. It was not enough.

  On the other hand, long-term followability to the use site is extremely important. For joint materials for working joints that require high durability, such as curtain walls for high-rise buildings, and for sealing materials for direct glazing, joint followability is required. In order to ensure, the adhesion-imparting agent is not included in the sealing material, and a construction method using a primer or the like is generally used in order to maintain the adhesiveness between the joints and gaps between various members over a long period of time. However, since the primer is a work process that is manually applied by the operator using a brush or the like, variations in application between the operators, uneven coating, or places where the primer is not sufficiently applied to the substrate In view of the purpose of imparting water tightness and air tightness, adhesion reliability is still regarded as a problem, and it has long been required that the sealant itself has self-adhesion performance.

JP-A-52-73998 Japanese Patent Laid-Open No. 5-125272 JP-A-3-72527 Japanese Patent Laid-Open No. 63-6003 JP 09-272714 A Japanese Patent Laid-Open No. 11-043512 JP 2000-154205 A

  An object of the present invention is to provide a curable composition that is excellent in mechanical properties and weather resistance after curing, and that can also realize excellent adhesiveness.

  As a result of intensive studies in view of the above-mentioned present situation, the present inventors have (meth) acrylic acid ester polymer (I) having at least one crosslinkable silyl group, at least one crosslinkable silyl group, A curable composition containing a specific (meth) acrylic acid ester and an organic polymer (II) having a solubility parameter (SP value) of 0.2 or greater than that of the (meth) acrylic acid ester polymer (I). The present inventors have found that the above problems can be improved by using a product, and have completed the present invention.

That is, the present invention is obtained by polymerizing (meth) acrylic acid ester having at least one crosslinkable silyl group represented by the general formula (1) and represented by the following general formula (2). acrylate ester polymer (I), and _{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ¹ or When two or more R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
_{CH 2 = C (R) COO} -R 3 (2)
(In the formula, R is a hydrogen atom or a methyl group, and R ³ is an organic group having 1 to 20 carbon atoms.)
20% by weight of (meth) acrylic acid ester having at least one crosslinkable silyl group represented by the general formula (1) and represented by the following general formula (3) and / or the following general formula (4) An organic polymer (II) obtained by polymerizing the above-described monomers and having a solubility parameter (SP value) of 0.2 or more greater than that of the (meth) acrylic acid ester polymer (I),
_{CH 2 = C (R) COO} -R 4 (3)
(In the formula, R is a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 3 carbon atoms.)
_{CH 2 = C (R) COO-} (R 5 -O-) n R 6 (4)
Wherein R is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms or an aralkylene group having 7 to 20 carbon atoms, and R ⁶ is hydrogen. (But only when n is 2 or more), 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, n is an integer of 1 or more, and n ) ^{May be} the same group or different from each other.
And a weight ratio (I) / (II) of the (meth) acrylic acid ester polymer (I) to the organic polymer (II) is 99/1 to 70/30.

  The (meth) acrylate polymer (I) is preferably polybutyl acrylate obtained by polymerizing butyl acrylate.

  (Meth) acrylic acid ester polymer (I) is (b1) an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms, (b2) an alkyl acrylate having an alkyl group having 4 to 7 carbon atoms, and (B3) It is preferable that the alkyl group is obtained by copolymerizing an alkyl acrylate having 8 to 20 carbon atoms.

  (B1) The total amount of alkyl acrylate having an alkyl group having 1 to 3 carbon atoms is 1 by weight with respect to the total amount of all (meth) acrylate monomers constituting the (meth) acrylate polymer. % To 30% and the total amount of (b2) alkyl acrylate having an alkyl group of 4 to 7 carbon atoms is the total of (meth) acrylate monomers constituting the (meth) acrylate polymer. (B3) The total amount of alkyl acrylate having an alkyl group of 8 to 20 carbon atoms in the weight ratio with respect to the total amount is 45% or more and 95% or less. The weight ratio is preferably 4% or more and 35% or less with respect to the total amount of the (meth) acrylate monomer.

  (B1) The total amount of alkyl acrylate having an alkyl group having 1 to 3 carbon atoms is 1 by weight with respect to the total amount of all (meth) acrylate monomers constituting the (meth) acrylate polymer. % Or more and 20% or less is preferable.

  (B2) The total amount of alkyl acrylate having an alkyl group of 4 to 7 carbon atoms is 50 by weight with respect to the total amount of all (meth) acrylate monomers constituting the (meth) acrylate polymer. % Or more and 95% or less, and more preferably 60% or more and 93% or less.

  (B3) The total amount of alkyl acrylate having an alkyl group of 8 to 20 carbon atoms is 6 by weight with respect to the total amount of all (meth) acrylic acid ester monomers constituting the (meth) acrylic acid ester polymer. % Or more and 25% or less is preferable.

  (B1) The alkyl acrylate having an alkyl group having 1 to 3 carbon atoms is preferably methyl acrylate and / or ethyl acrylate.

  (B2) The alkyl acrylate having an alkyl group having 4 to 7 carbon atoms is preferably butyl acrylate.

  (B3) The alkyl acrylate having an alkyl group of 8 to 20 carbon atoms is preferably dodecyl acrylate and / or octadecyl acrylate.

  The number average molecular weight of the (meth) acrylic acid ester polymer (I) measured by gel permeation chromatography is preferably 5,000 to 80,000, more preferably 8,000 to 50,000. .

  The (meth) acrylate polymer (I) is preferably a polymer having a ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography of less than 1.8.

  The (meth) acrylic acid ester polymer (I) is preferably produced by atom transfer radical polymerization.

  The organic polymer (II) is a copolymer obtained by copolymerizing a (meth) acrylic acid ester represented by the general formula (3) and / or the general formula (4) and another monomer. preferable.

  The other monomer is preferably a vinyl monomer.

  The (meth) acrylic acid ester represented by the general formula (3) of the organic polymer (II) is preferably methyl acrylate, ethyl acrylate, or methyl methacrylate.

  The (meth) acrylic acid ester represented by the general formula (4) of the organic polymer (II) is preferably 2-methoxyethyl acrylate.

  A polymer having a number average molecular weight of 500 to 20000 as measured by gel permeation chromatography of the organic polymer (II) is preferred.

  It is preferable that the organic polymer (II) is produced by free radical polymerization.

  It is preferable that the organic polymer (II) is produced by atom transfer radical polymerization.

  The crosslinkable silyl group of the organic polymer (II) is preferably at the end.

  Furthermore, it is preferable to contain a polyether polymer (III) represented by the general formula (1) and having at least one crosslinkable functional group.

  The number average molecular weight measured by gel permeation chromatography of the polyether polymer (III) is preferably 5000 or more.

  It is preferable that the main chain of the polyether polymer (III) is essentially polypropylene oxide.

  The crosslinkable functional group of the polyether polymer (III) is preferably a crosslinkable silyl group.

  The present invention relates to a curable composition characterized in that a molded product obtained by curing the composition described above has good adhesion to a substrate coated with a thermoplastic fluororesin.

  The present invention relates to a molded product obtained by curing the composition described above.

  The present invention relates to a sealing material using the curable composition described above.

  The present invention relates to an adhesive using the curable composition described above.

  The present invention relates to a liquid gasket using the curable composition described above.

  The present invention relates to a sealing material for multilayer glass using the curable composition described above.

  In the curable composition containing the (meth) acrylic acid ester polymer (I) having a crosslinkable silyl group, a group obtained by using an organic polymer (II) having a solubility parameter 0.2 or more larger than that of (I) The present invention relates to a method for improving adhesion to a material.

  The present invention provides a curable composition that is excellent in mechanical properties and weather resistance after curing, and that can also realize excellent adhesion to a high-temperature baked fluorinated aluminum substrate or an acrylic substrate.

The present invention has (meth) acrylic acid obtained by polymerizing a (meth) acrylic acid ester having at least one crosslinkable silyl group represented by the general formula (1) and represented by the following general formula (2). ester polymer (I), and _{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ¹ or When two or more R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
_{CH 2 = C (R) COO} -R 3 (2)
(In the formula, R is a hydrogen atom or a methyl group, and R ³ is an organic group having 1 to 20 carbon atoms.)
20% by weight of (meth) acrylic acid ester having at least one crosslinkable silyl group represented by the general formula (1) and represented by the following general formula (3) and / or the following general formula (4) An organic polymer (II) obtained by polymerizing the above-described monomers and having a solubility parameter (SP value) of 0.2 or more greater than that of the (meth) acrylic acid ester polymer (I),
_{CH 2 = C (R) COO} -R 4 (3)
(In the formula, R is a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 3 carbon atoms.)
_{CH 2 = C (R) COO-} (R 5 -O-) n R 6 (4)
Wherein R is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms or an aralkylene group having 7 to 20 carbon atoms, and R ⁶ is hydrogen. (But only when n is 2 or more), 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, n is an integer of 1 or more, and n ) ^{May be} the same group or different from each other.
And a weight ratio (I) / (II) of the (meth) acrylic acid ester polymer (I) to the organic polymer (II) is 99/1 to 70/30.

<< (Meth) acrylic acid ester polymer (I) >>
<Main chain of (meth) acrylate polymer>
The (meth) acrylic acid ester represented by the following general formula (2) constituting the main chain of the (meth) acrylic acid ester polymer (I) having a crosslinkable silyl group in the present invention is not particularly limited, Various things can be used.
_{CH 2 = C (R) COO} -R 3 (2)
(In the formula, R is a hydrogen atom or a methyl group, and R ³ is an organic group having 1 to 20 carbon atoms.)

  Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) S-butyl acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid alicyclic such as tridecyl and alkyl (meth) acrylates such as stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and tricyclodecynyl (meth) acrylate Alkyl, 2-methoxyethyl (meth) acrylate, dimethyl (meth) acrylate Heteroatom-containing (meth) such as ruaminoethyl, chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate, polypropylene glycol (meth) acrylate, glycidyl (meth) acrylate Acrylic acid esters may be mentioned, but ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and 2-methoxybutyl acrylate are preferred, and butyl acrylate is more preferred.

  The (meth) acrylic acid ester polymer (I) is preferably polybutyl acrylate obtained by polymerizing butyl acrylate from the viewpoint of weather resistance.

  The (meth) acrylate polymer (I) includes (b1) an alkyl acrylate having an alkyl group of 1 to 3 carbon atoms, and (b2) an alkyl acrylate having an alkyl group of 4 to 7 carbon atoms. And (b3) that is obtained by copolymerizing an alkyl acrylate having an alkyl group of 8 to 20 carbon atoms is preferred from the viewpoints of viscosity and cured product mechanical properties.

  (B1) As an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms, methyl acrylate and / or ethyl acrylate is preferable. (B2) As an alkyl acrylate having an alkyl group having 4 to 7 carbon atoms, Butyl acrylate is preferred, and (b3) alkyl acrylate having an alkyl group of 8 to 20 carbon atoms is preferably dodecyl acrylate and / or octadecyl acrylate.

  (B1) The total amount of alkyl acrylate having an alkyl group having 1 to 3 carbon atoms is 1 by weight with respect to the total amount of all (meth) acrylate monomers constituting the (meth) acrylate polymer. % To 30% and the total amount of (b2) alkyl acrylate having an alkyl group of 4 to 7 carbon atoms is the total of (meth) acrylate monomers constituting the (meth) acrylate polymer. (B3) The total amount of alkyl acrylate having an alkyl group of 8 to 20 carbon atoms in the weight ratio with respect to the total amount is 45% or more and 95% or less. The weight ratio is preferably 4% or more and 35% or less with respect to the total amount of the (meth) acrylate monomer.

  (B1) The total amount of alkyl acrylate having an alkyl group having 1 to 3 carbon atoms is expressed in a weight ratio with respect to the total amount of all (meth) acrylic acid ester monomers constituting the (meth) acrylic acid ester polymer. It is more preferably 1% or more and 20% or less.

  (B2) The total amount of alkyl acrylate having an alkyl group having 4 to 7 carbon atoms is expressed in a weight ratio with respect to the total amount of all (meth) acrylate monomers constituting the (meth) acrylate polymer. It is more preferably 50% or more and 95% or less, and further preferably 60% or more and 93% or less.

  (B3) The total amount of alkyl acrylate having an alkyl group of 8 to 20 carbon atoms is expressed in a weight ratio with respect to the total amount of all (meth) acrylate monomers constituting the (meth) acrylate polymer. More preferably, it is 6% or more and 20% or less.

  The molecular weight distribution of the (meth) acrylate polymer (I) having a crosslinkable silyl group in the present invention, that is, the weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC). ) Ratio (Mw / Mn) is not particularly limited, but is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, and even more preferably 1. 5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. If the molecular weight distribution is too large, the viscosity at the molecular weight between the same cross-linking points increases and the handling tends to be difficult. In the GPC measurement in the present invention, chloroform is used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  The number average molecular weight of the vinyl polymer (I) having a crosslinkable silyl group in the present invention is not particularly limited, but is preferably 5,000 to 80,000, preferably 8,000 to 50, when measured by GPC. 000 is more preferable. If the molecular weight is too low, the original characteristics of the vinyl polymer (b) tend to be difficult to be expressed. On the other hand, if the molecular weight is too high, handling tends to be difficult.

<Synthesis of (meth) acrylic acid ester polymer>
The (meth) acrylic acid ester-based polymer (I) having a crosslinkable silyl group used in the present invention can be obtained by various polymerization methods, and is not particularly limited, but the versatility of the monomer, ease of control, etc. In view of the above, the radical polymerization method is preferable, and among the radical polymerizations, controlled radical polymerization is more preferable. This controlled radical polymerization method can be classified into a “chain transfer agent method” and a “living radical polymerization method”. Living radical polymerization that allows easy control of the molecular weight and molecular weight distribution of the resulting (meth) acrylic acid ester-based polymer (I) having a crosslinkable silyl group is more preferred, the availability of raw materials, and the functional group at the end of the polymer Atom transfer radical polymerization is particularly preferred because of its ease of introduction. The radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods. For example, JP-A-2005-232419 and JP-A-2005-234419 The description of 2006-291073 gazette etc. can be referred to.

  The atom transfer radical polymerization, which is one of the preferred methods for synthesizing the (meth) acrylic acid ester polymer (I) having a crosslinkable silyl group in the present invention, will be briefly described below.

  In atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a sulfonyl halide. A compound or the like is preferably used as an initiator. Specific examples include compounds described in paragraphs [0040] to [0064] of JP-A-2005-232419.

  In order to obtain a vinyl polymer having two or more alkenyl groups capable of hydrosilylation in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. preferable.

  There is no restriction | limiting in particular as a (meth) acrylic-ester type monomer used in atom transfer radical polymerization, All the (meth) acrylic-ester type monomers illustrated above can be used suitably.

  Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal, More preferably, it is 0. A transition metal complex having valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal, particularly preferably a copper complex. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. In the case of using a copper compound, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity These polyamines are added as ligands.

The polymerization reaction can be carried out without solvent, but can also be carried out in various solvents. It does not specifically limit as a kind of solvent, The solvent of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0067] is mentioned. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium.

  Although superposition | polymerization temperature is not limited, It can carry out in the range of 0-200 degreeC, Preferably, it is the range of room temperature-150 degreeC.

<Crosslinkable silyl group>
The crosslinkable silyl group of the present invention has the general formula (1);
_{- [Si (R) 2-} b (Y) b O] m -Si (R 1) 3-a (Y) a (1)
{In the formula, R and R ¹ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ') ₃ SiO- (R' Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different, and represents a triorganosiloxy group represented by R or R ¹ When two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
It is group represented by these.

  Examples of the hydrolyzable group include commonly used groups such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group, an amide group, and an aminooxy group are preferable, but an alkoxy group is particularly preferable in terms of mild hydrolyzability and easy handling. Among the alkoxy groups, those having fewer carbon atoms have higher reactivity, and the reactivity decreases in the order of methoxy group> ethoxy group> propoxy group, and can be selected according to the purpose and application.

Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + Σb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming the crosslinkable silyl group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less. In particular, the general formula (5)
-Si (R ² ) _3-a (Y) _a (5)
(Wherein R ² and Y are the same as described above, a is an integer of 1 to 3)
Is preferable because it is easily available.

  Although not particularly limited, a is preferably 2 or more in consideration of curability.

  As such a vinyl polymer having a crosslinkable silyl group, a polymer having a hydrolyzable silicon group formed by bonding two hydrolyzable groups per silicon atom is often used. When a very fast curing rate is required, such as when used at low temperatures, etc., the curing rate is not sufficient, and if it is desired to provide flexibility after curing, it is necessary to reduce the crosslinking density. For this reason, the crosslink density is not sufficient, and stickiness (surface tack) may occur. In that case, it is preferable that a is 3 (for example, trimethoxy functional group).

  Further, those having a of 3 (for example, trimethoxy functional group) cure faster than those having 2 (for example, dimethoxy functional group), but those having 2 are superior in terms of storage stability and mechanical properties (elongation, etc.). There is a case. In order to balance the curability and physical properties, two (for example, dimethoxy functional group) and three (for example, trimethoxy functional group) may be used in combination.

  For example, when Y is the same, the greater the a, the higher the reactivity of Y. Therefore, by variously selecting Y and a, it is possible to control the curability and the mechanical properties of the cured product. It can be selected according to the application. A compound having a of 1 is used as a chain extender mixed with a polymer having a crosslinkable silyl group, specifically, at least one polymer comprising a polysiloxane, polyoxypropylene or polyisobutylene. it can. It is possible to obtain a composition having low viscosity before curing, high elongation at break after curing, low bleeding, low surface contamination, and excellent paint adhesion.

  The number of crosslinkable silyl groups in the (meth) acrylic acid ester polymer (I) having a crosslinkable silyl group is not particularly limited, but from the viewpoint of the curability of the composition and the physical properties of the cured product, The average number is 1 or more, preferably 1.1 or more and 4.0 or less, more preferably 1.2 or more and 3.5 or less.

  When a rubber property is particularly required for a cured product obtained by curing the curable composition of the present invention, the molecular weight between crosslinking points that greatly affects rubber elasticity can be increased. One is preferably at the end of the molecular chain. More preferably, it has all crosslinkable functional groups at the molecular chain ends.

  A method for producing a (meth) acrylic acid ester polymer having a crosslinkable silyl group at the molecular chain terminal is disclosed in JP-B-3-14068, JP-B-4-55444, JP-A-6-221922, and the like. Is disclosed. However, since these methods are free radical polymerization methods using the above-mentioned “chain transfer agent method”, the resulting polymer has a relatively high proportion of crosslinkable silyl groups at the molecular chain ends, while Mw / Mn The value of the molecular weight distribution represented by is generally as large as 2 or more, and the viscosity is increased. Therefore, in order to obtain a vinyl polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable silyl group at the molecular chain terminal at a high ratio, the above “living radical polymerization method” is used. However, it is not limited to a polymer having a narrow molecular weight distribution.

<Introduction method of crosslinkable silyl group>
As a method for introducing a crosslinkable silyl group into the obtained (meth) acrylic acid ester polymer, a known method can be used. For example, the method of Paragraph [0083]-[117] of Unexamined-Japanese-Patent No. 2007-302749 is mentioned. Among these methods, (A) a hydrosilane compound having a crosslinkable silyl group is added to a (meth) acrylic acid ester polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst. The method of adding is preferable.

  Here, a method for adding a hydrosilane compound having a crosslinkable silyl group to a (meth) acrylic acid ester-based polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst, which is one of preferable introduction methods, is described below. Briefly described. In this method, a (meth) acrylate polymer obtained by living radical polymerization of a (meth) acrylate monomer is a compound having at least two low-polymerizable alkenyl groups (hereinafter referred to as “diene compound”). And a hydrosilane compound having a crosslinkable silyl group is added to the vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst.

The (meth) acrylic acid ester polymer having at least one alkenyl group used in the method (A) can be obtained by various methods. Although the synthesis method is illustrated below, it is not necessarily limited to these.
(Aa) When synthesizing a (meth) acrylic acid ester polymer by radical polymerization, for example, a polymerizable alkenyl group and low polymerizability in one molecule as listed in the following general formula (6) A method in which a compound having an alkenyl group is reacted as a second monomer.
^{_{H 2 C = C (R 8}} ) -R 9 -R 10 -C (R 11) = CH 2 (6)
(Wherein R ⁸ represents hydrogen or a methyl group, R ⁹ represents —C (O) O—, or o-, m-, p-phenylene group, R ¹⁰ represents a direct bond, 20 represents a divalent organic group having 20 and may contain one or more ether bonds, R ¹¹ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. Represents -20 aralkyl groups)
There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. It is preferable to react as the second monomer at the end or after completion of the reaction of the predetermined monomer.

  (Ab) When synthesizing a (meth) acrylic acid ester polymer by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, at the end of the polymerization reaction or after completion of the reaction of the predetermined monomer, A method of reacting a compound having at least two alkenyl groups having low polymerizability such as 1,9-decadiene.

  (Ac) Various kinds of (meth) acrylic acid ester-based polymers having at least one highly reactive carbon-halogen bond having an alkenyl group such as organic tin such as allyltributyltin and allyltrioctyltin The halogen metal is substituted by reacting the organometallic compound.

(Ad) A stabilized carbanion having an alkenyl group as shown in the general formula (7) is reacted with a (meth) acrylic acid ester polymer having at least one highly reactive carbon-halogen bond. Method to replace halogen.
^{M + C - (R 12)} (R 13) -R 14 -C (R 11) = CH 2 (7)
(Wherein, R ¹¹ is the same, R ^12, R ¹³ together carbanion C ^- or an electron withdrawing group stabilizing, or one of the other is hydrogen or a 1 to 10 carbon atoms in the electron-withdrawing group Represents an alkyl group or a phenyl group, R ¹⁴ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may contain one or more ether bonds, M ⁺ represents an alkali metal ion, Or a quaternary ammonium ion)
As the electron-withdrawing group for R ¹² and R ¹³ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

  (Ae) An enolate anion is prepared by allowing a metal simple substance or an organometallic compound such as zinc to act on a (meth) acrylic acid ester-based polymer having at least one highly reactive carbon-halogen bond. Thereafter, an electrophilic compound having an alkenyl group such as an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group, etc. A method of reacting with a compound.

(Af) An oxyanion or carboxylate anion having an alkenyl group as represented by the general formula (8) or (9) is added to a vinyl polymer having at least one highly reactive carbon-halogen bond. A method of replacing halogen by reaction.
^{_{H 2 C = C (R 11}} ) -R 15 -O - M + (8)
(Wherein R ¹¹ and M ⁺ are the same as above. R ¹⁵ is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
H ₂ C═C (R ¹¹ ) —R ¹⁶ —C (O) O ⁻ M ⁺ (9)
(In the formula, R ¹¹ and M ⁺ are the same as above. R ¹⁶ may be a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.)
Etc.

  The method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond is an atom transfer radical polymerization method using an organic halide as described above as an initiator and a transition metal complex as a catalyst. For example, but not limited to.

Further, the (meth) acrylic acid ester polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used, but are not limited thereto. I don't mean. In the hydroxyl group of the (meth) acrylic acid ester polymer having at least one hydroxyl group,
(Ag) A method of reacting a base such as sodium methoxide with an alkenyl group-containing halide such as allyl chloride.

  (Ah) A method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate.

  (Ai) A method in which an alkenyl group-containing acid halide such as (meth) acrylic acid chloride is reacted in the presence of a base such as pyridine.

  (Aj) A method in which an alkenyl group-containing carboxylic acid such as acrylic acid is reacted in the presence of an acid catalyst;

  In the present invention, when halogen is not directly involved in the method of introducing an alkenyl group such as (Aa) and (Ab), a (meth) acrylate polymer is synthesized using a living radical polymerization method. It is preferable to do. The method (Ab) is more preferable from the viewpoint of easier control.

  When introducing an alkenyl group by converting halogen in a (meth) acrylic acid ester polymer having at least one highly reactive carbon-halogen bond, it has at least one highly reactive carbon-halogen bond. Highly reactive carbon at the terminal obtained by radical polymerization of (meth) acrylic acid ester monomers (atom transfer radical polymerization method) using organic halides or sulfonyl halide compounds as initiators and transition metal complexes as catalysts. It is preferable to use a (meth) acrylic acid ester polymer having at least one halogen bond. In view of easier control, the method (Af) is more preferable.

Moreover, there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group, When a typical thing is shown, the compound shown by General formula (10) will be illustrated.
_{^{H- [Si (R 17) 2}} -b (Y) b O] m -Si (R 18) 3-a (Y) a (10)
{Wherein R ¹⁷ and R ¹⁸ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different, and represents a triorganosiloxy group represented by R ¹³ or When two or more R ¹⁴ are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }

Among these hydrosilane compounds, in particular, the general formula (11)
H-Si (R ¹⁷ ) _3-a (Y) _a (11)
(Wherein R ¹⁷ and Y are the same as defined above, and a is an integer of 1 to 3)
The compound which has a crosslinkable group shown by is preferable from a point with easy acquisition.

When the hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. Examples of the transition metal catalyst include platinum simple substance, alumina, silica, carbon black and the like in which a platinum solid is dispersed, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin. Complex, platinum (0) -divinyltetramethyldisiloxane complex is mentioned. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2, TiCl 4 , and the like.

<Use of a plurality of (meth) acrylic acid ester polymers>
The above-mentioned (meth) acrylic acid ester polymer can be used alone, or two or more (meth) acrylic acid ester polymers can be used in combination. When only one kind is used, it is preferable to use a vinyl polymer having a molecular weight of 5,000 to 80,000 and a number of crosslinkable silyl groups of 1.2 to 3.5. When combining two or more types of vinyl polymers, the first polymer is a vinyl polymer having a molecular weight of 5,000 to 80,000 and a number of crosslinkable silyl groups of 1.2 to 3.5, When the second polymer is a polymer having a small number of crosslinkable silyl groups, a cured product having high elongation at break, low bleeding, low surface contamination, and excellent paint adhesion can be obtained. Moreover, the viscosity of a composition can be reduced by setting the molecular weight of a 2nd polymer smaller. The preferred molecular weight of the polymer to be the low molecular weight component is less than 10,000, more preferably less than 5,000, and the preferred number of crosslinkable silyl groups is less than 1.2, further 1 or less. Further, since the viscosity can be further reduced, the molecular weight distribution is preferably less than 1.8. When a (meth) acrylic acid ester polymer having a crosslinkable functional group and a molecular weight distribution of 1.8 or more and a vinyl polymer having a crosslinkable silyl group at one end are added, the effect of reducing the viscosity is remarkable.

  As such a polymer having a low molecular weight and a small number of crosslinkable silyl groups, it is sure to use a (meth) acrylic acid ester polymer having a crosslinkable silyl group at one end obtained by the following production method. It is preferable because a crosslinkable silyl group can be introduced.

  The (meth) acrylic acid ester-based polymer having a crosslinkable silyl group at one end has approximately one crosslinkable silyl group per molecule at the polymer end. Use of the above-mentioned living radical polymerization method, particularly the atom transfer radical polymerization method, has a high proportion of crosslinkable silyl groups at the molecular chain ends, a molecular weight distribution of less than 1.8, a narrow molecular weight distribution, and a low viscosity. Since a (meth) acrylic ester polymer is obtained, it is preferable.

  About the method of introduce | transducing a crosslinkable silyl group into one terminal, the method shown below can be used, for example. In the method of introducing a crosslinkable silyl group, an alkenyl group, and a hydroxyl group by terminal functional group conversion, these functional groups can be precursors to each other, and therefore, are described in the order starting from the method of introducing the crosslinkable silyl group.

(1) A method of adding a hydrosilane compound having a crosslinkable silyl group to a polymer having one alkenyl group per molecule at the molecular chain end in the presence of a hydrosilylation catalyst,
(2) A method of reacting a polymer having one hydroxyl group per molecular chain end with a compound having both a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule,
(3) A method of reacting a polymer having one highly reactive carbon-halogen bond per molecule at the end of a molecular chain with a compound having a crosslinkable silyl group and a stable carbanion in one molecule,
Etc.

  Polymers having one alkenyl group per molecule chain end in the method (1) can be obtained by various methods. Although a manufacturing method is illustrated below, it is not necessarily limited to these.

  (1-1) Various polymers having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin in a polymer having one highly reactive carbon-halogen bond per molecular chain end A method of replacing halogen by reacting an organometallic compound.

(1-2) A polymer having one highly reactive carbon-halogen bond per molecule per molecule is reacted with a stabilized carbanion having an alkenyl group as shown in the general formula (12) to form a halogen. How to replace
^{M + C - (R 18)} (R 19) -R 20 -C (R 21) = CH 2 (12)
(In the formula, R ¹⁸ and R ¹⁹ are both electron-withdrawing groups that stabilize carbanion C-, or one is the electron-withdrawing group and the other is hydrogen or an alkyl group having 1 to 10 carbon atoms, or a phenyl group. R ²⁰ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms and may contain one or more ether bonds R ²¹ represents hydrogen or an alkyl group having 1 to 20 carbon atoms Represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and M + represents an alkali metal ion or a quaternary ammonium ion.)
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

  (1-3) An enolate anion is prepared by reacting a polymer having one highly reactive carbon-halogen bond per molecule chain molecule with a single metal such as zinc or an organometallic compound, for example, Thereafter, an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group, etc. How to react with.

(1-4) a polymer having one highly reactive carbon-halogen bond per molecule per molecule, for example, an oxyanion having an alkenyl group as shown in the general formula (13) or (14) A method of substituting halogen by reacting a carboxylate anion.
^{_{H 2 C = C (R 21}} ) -R 22 -O - M + (13)
(In the formula, R ²¹ and M + are the same as above. R ²² is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
H ₂ C═C (R ²¹ ) —R ²³ —C (O) O ⁻ M ⁺ (14)
(In the formula, R ²¹ and M + are the same as above. R ²³ is a direct bond or a divalent organic group having 1 to 20 carbon atoms, and may contain one or more ether bonds.)
Etc.

  The above-described method for synthesizing a polymer having one highly reactive carbon-halogen bond per molecule at the end of a molecule chain is an atom transfer using an organic halide as described above as an initiator and a transition metal complex as a catalyst. Examples include, but are not limited to, radical polymerization methods.

  Further, a polymer having one alkenyl group per molecule at the molecular chain end can be obtained from a polymer having at least one hydroxyl group at the molecular chain end, and the methods exemplified below can be used, but are not limited thereto. It is not done.

In the polymer hydroxyl group having at least one hydroxyl group at the molecular chain end,
(1-5) a method of reacting a base such as sodium methoxide with an alkenyl group-containing halide such as allyl chloride;
(1-6) a method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate,
(1-7) a method of reacting an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine,
(1-8) A method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst.

  When an alkenyl group is introduced by converting a halogen of a polymer having one highly reactive carbon-halogen bond per molecule at the end of the molecule chain, one highly reactive carbon-halogen bond per molecule A highly reactive carbon-halogen bond is formed at the terminal obtained by radical polymerization (atom transfer radical polymerization) of a vinyl monomer using an organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. It is preferable to use a polymer having one molecule per molecule chain end.

Moreover, there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group, When a typical thing is shown, the compound shown by General formula (15) will be illustrated.
H- [Si (R ¹⁷ _2-b ) (Y _b ) O] _m -Si (R ¹⁸ _3-a ) Y _a (15)
(In the formula, R ¹⁷ , R ¹⁸ , Y, a, b and m are the same as described above. When two or more R ¹⁷ or R ¹⁸ are present, they may be the same or different. However, it shall be satisfied that a + mb ≧ 1.)
Among these hydrosilane compounds, in particular, the general formula (16)
H-Si (R ¹⁷ _3-a ) Y _a (16)
(Wherein R ¹⁷ , Y and a are the same as above)
The compound which has a crosslinkable silyl group shown by is preferable from a point with easy acquisition.

When the hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. Examples of the transition metal catalyst include platinum simple substance, alumina, silica, carbon black and the like in which a platinum solid is dispersed, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin. Complex, platinum (0) -divinyltetramethyldisiloxane complex is mentioned. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2, TiCl 4 and the like.

  The amount of the (meth) acrylate polymer having a crosslinkable silyl group at one end, preferably a polymer having a molecular weight distribution of less than 1.8, is 100 parts by weight of a (meth) acrylate polymer. On the other hand, the amount is preferably 5 to 400 parts by weight from the viewpoint of modulus and elongation.

  As a second embodiment in which two or more kinds of (meth) acrylic acid ester polymers are used in combination, a molecular weight distribution of 1.8 or more (meth) acrylic acid ester polymers and a molecular weight distribution of less than 1.8 Combinations of (meth) acrylic acid ester polymers can also be used. A vinyl polymer having a molecular weight distribution of 1.8 or more may or may not have a crosslinkable silicon group, but having a crosslinkable silicon group is preferred because weather resistance, adhesive strength, and strength at break are further improved. Moreover, the improvement of the tear strength of the hardened | cured material of a composition can be anticipated. A (meth) acrylic acid ester having a molecular weight distribution of less than 1.8, used as a first polymer, a (meth) acrylic acid ester polymer having a molecular weight distribution of 1.8 or more, or a second polymer. As the main chain of the polymer, a polymer derived from the (meth) acrylic acid ester monomer described above can be used, and both polymers are preferably acrylic acid ester polymers.

  A vinyl polymer having a molecular weight distribution of 1.8 or more can be obtained by a usual polymerization method, for example, a solution polymerization method by radical reaction. The polymerization is usually carried out by adding the above-mentioned monomer, a radical initiator, a chain transfer agent and the like and reacting at 50 to 150 ° C. In this case, generally a molecular weight distribution of 1.8 or more is obtained.

  Examples of the radical initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyanovaleric) acid. 1,1′-azobis (1-cyclohexanecarbonitrile), azobisisobutyric acid amidine hydrochloride, 2,2′-azobis (2,4-dimethylvaleronitrile) and other azo initiators, benzoyl peroxide, diperoxide Organic peroxide-based initiators such as -tert-butyl are exemplified, but use of azo-based initiators is preferable in that they are not affected by the solvent used for polymerization and have a low risk of explosion and the like.

  Examples of chain transfer agents include n-dodecyl mercaptan, tert-dodecyl mercaptan, lauryl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyl Examples include mercaptans such as diethoxysilane and halogen-containing compounds.

  The polymerization may be performed in a solvent. Examples of the solvent are preferably nonreactive solvents such as ethers, hydrocarbons, and esters.

Examples of the method for introducing a crosslinkable silyl group include a method of copolymerizing a compound having both a polymerizable unsaturated bond and a crosslinkable silyl group with a (meth) acrylate monomer unit. The compound having both a polymerizable unsaturated bond and a crosslinkable silyl group is represented by the general formula (17):
^{_{CH 2 = C (R 21)}} COOR 24 - [Si (R 17 2-b) (Y b) O] m Si (R 18 3-a) Y a (17)
(In the formula, R ²¹ is the same as above. R ²⁴ is a divalent alkylene group having 1 to 6 carbon atoms. Y, a, b, and m are the same as above.)
Or general formula (18):
^{_{CH 2 = C (R 21)}} - [Si (R 17 2-b) (Y b) O] m Si (R 18 3-a) Y a (18)
(In the formula, R ²¹ , R ¹⁷ , R ¹⁸ , Y, a, b and m are the same as above.)
Monomers such as γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl polyalkoxysilane such as γ-methacryloxypropyltriethoxysilane, and γ-acrylic. Γ-acryloxypropyl polyalkoxysilane such as loxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, etc. Examples thereof include vinyl alkyl polyalkoxysilane. Further, when a compound having both a mercapto group and a crosslinkable silyl group is used as a chain transfer agent, the crosslinkable silyl group can be introduced into the polymer terminal. Examples of such chain transfer agents include mercaptans such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane. .

<< Organic polymer (II) having at least one crosslinkable silyl group >>
When the organic polymer (II) having at least one crosslinkable silyl group is added to the (meth) acrylic acid ester polymer (I), the adhesion with the substrate is improved, and in particular, the thermoplastic fluororesin is coated. Adhesiveness to the substrate is improved.

The organic polymer (II) having at least one crosslinkable silyl group has at least one crosslinkable silyl group represented by the general formula (1) and has the following general formula (3) and / or the following general formula (4). The solubility parameter (SP value) obtained by polymerizing a monomer containing 20% or more by weight of the (meth) acrylic acid ester represented by () is 0 from the (meth) acrylic acid ester polymer (I). The organic polymer is not particularly limited as long as the organic polymer is 2 or larger.
_{CH 2 = C (R) COO} -R 4 (3)
(In the formula, R is a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 3 carbon atoms.)
_{CH 2 = C (R) COO-} (R 5 -O-) n R 6 (4)
Wherein R is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms or an aralkylene group having 7 to 20 carbon atoms, and R ⁶ is hydrogen. (But only when n is 2 or more), 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, n is an integer of 1 or more, and n ) ^{May be} the same group or different from each other.
When the hydrolyzable silyl group is hydrolyzed to form a siloxane bond, the organic polymer is crosslinked to form a rubber-like cured product.

The solubility parameter (SP value) was measured using Polym. Eng. Sci. (Polymer Engineering Science), 14 (2), 147 (1974). F. It is obtained from the Fedors equation. Specifically, the solubility parameter (SP value) of the structural unit based on each monomer constituting the (meth) acrylic acid ester polymer (I) and the organic polymer (II) is expressed by the following formula (20). Is a constant specific to a substance depending on temperature.
Solubility parameter (SP value) = (ΔE / V) ^1/2 (20)
(However, ΔE: molecular cohesive energy, V: molecular volume.)
The SP value of the structural unit based on each monomer is a structure in which the monomer is polymerized and exists in the polymer chain, that is, if the vinyl monomer is used, the double bond is opened. As a structure having a single bond, R.I. F. This is calculated from ΔE, V in the Fedors equation and corresponds to the SP value of the homopolymer of the monomer.

The solubility parameter (SP value) of the (meth) acrylic acid ester polymer (I) and the organic polymer (II) is the i-th monomer Mi (i is 1 to 1) constituting this polymer. n (integer of n) in a polymer (ni represents the molar fraction of the monomer Mi (the meaning of the suffix [i] is the same hereinafter)), and based on the monomer. From the solubility parameter (SPi) of the structural unit, it can be calculated by the following formula (21).
Solubility parameter (SP value) = Σ (SPi × ni) (21)

  By using the organic polymer (II) having a solubility parameter (SP value) of 0.2 or more larger than that of the (meth) acrylic acid ester polymer (I), the (meth) acrylic acid ester polymer (I) is used. ), And good adhesiveness is exhibited. In particular, it exhibits good adhesion to a substrate coated with a thermoplastic fluororesin. When the solubility parameter (SP value) is less than 0.2 with respect to the (meth) acrylic acid ester polymer (I), a sufficient adhesive expression effect cannot be obtained.

  As the crosslinkable silyl group represented by the general formula (1), the same as those described in the part of the (meth) acrylic acid ester polymer (I) can be used.

  The main chain structure of the organic polymer (II) having at least one crosslinkable silyl group is not particularly limited, and is a polyether main chain structure, a polyester main chain structure, a polycarbonate main chain structure, a polyurethane main chain structure, a polyamide main chain. Structure, polyurea main chain structure, polyimide main chain structure, polysiloxane main chain structure, vinyl polymer main chain structure obtained by polymerizing polymerizable unsaturated groups, etc., and further obtained by combining these structures However, vinyl polymers such as hydrocarbon polymers and (meth) acrylic polymers obtained by polymerizing polymerizable unsaturated groups are preferred, and (meth) acrylic heavy polymers are preferred. A coalescence is more preferred, and a (meth) acrylic acid ester polymer is more preferred.

  The organic polymer (II) is preferably 0.2 or more than the solubility parameter (SP value) of the (meth) acrylic acid ester polymer (I), and the (meth) acrylic acid ester polymer (I) Those having miscibility but low compatibility are preferred because more organic polymer (II) is present at the interface of the substrate after curing than those having good compatibility, thereby improving adhesion.

From the above viewpoint, the main chain structure of the organic polymer (II) contains (meth) acrylic acid ester represented by the following general formula (3) and / or the following general formula (4) in a weight ratio of 20% or more. To do.
_{CH 2 = C (R) -COO} -R 4 (3)
(In the formula, R is a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 3 carbon atoms.)
_{CH 2 = C (R) COO-} (R 5 -O-) n R 6 (4)
Wherein R is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms or an aralkylene group having 7 to 20 carbon atoms, and R ⁶ is hydrogen. (But only when n is 2 or more), 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, n is an integer of 1 or more, and n When R is 2 or more, R ¹ may be the same group or different.)

  Specific examples of the (meth) acrylic acid ester represented by the general formula (3) include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid. Isopropyl is mentioned. These can be used alone or in combination of two or more. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are preferred from the viewpoints of compatibility with the (meth) acrylate polymer (I) and self-adhesion.

Specific examples of the ether structure-containing acrylate ester represented by the general formula (4) include the following. That is, when n in the chemical formula — (R ⁵ —O—) nR ⁶ representing an alcohol residue in the acrylate ester is 1, specific examples of the group include 2-methoxyethyl, 2-ethoxyethyl, 2-normal butoxyethyl, 2-isobutoxyethyl, 2-tertiary butoxyethyl, 2-dicyclopentenyloxyethyl, 2-phenoxyethyl, 2-methoxypropyl, 2-normalbutoxypropyl, 3-methoxybutyl, 4- Examples include methoxybutyl, 4-ethoxybutyl, 4-normal butoxybutyl, 4-isobutoxybutyl, 4-tertiary butoxybutyl, 4-dicyclopentenyloxybutyl and 4-phenoxybutyl. In the case where n = 2 or more, the R ⁶ moiety is hydrogen, methyl, ethyl, normal butyl, tertiary butyl and phenyl, and the (R ⁵ —O—) moiety is ethylene glycol, propylene glycol, 1,2- There are various combinations of butylene glycol and 1,4-butylene glycol. The compounds listed here are merely examples, and other alcohol residues having an ether bond may be used.

  In the ether structure-containing (meth) acrylic acid ester represented by the general formula (4), R is a hydrogen atom or a methyl group. However, the fact that it is a hydrogen atom lowers the Tg and reduces the viscosity of the organic polymer (II). It is preferable because it lowers.

  These can be used alone or in combination of two or more. Among these, from the viewpoint of compatibility with the vinyl polymer (I) and self-adhesion, a compound of n = 1 is preferable, and 2-methoxyethyl acrylate is most preferable.

  The organic polymer (II) is preferably a copolymer obtained by copolymerizing the (meth) acrylic acid ester and another monomer.

  The monomer that is copolymerized with the (meth) acrylic acid ester and / or the acrylic acid ester is not particularly limited, and various monomers can be used, but a vinyl monomer is preferable. It is more preferable to use a (meth) acrylic acid ester monomer constituting the (meth) acrylic acid ester polymer (I). By copolymerizing with the acrylate ester having the above polyether structure, it is miscible with the (meth) acrylate polymer (I) but is incompatible.

  The amount of the (meth) acrylic acid ester represented by the above general formulas (3) and (4) is 20% or more by weight, but is preferably 25% to 80%. If it is 20% or less, the compatibility with the (meth) acrylic acid ester polymer (I) is improved and the adhesiveness is lowered.

  The number average molecular weight of the organic polymer (II) of the present invention is not particularly limited, but it is preferably in the range of 500 to 20000 when measured by gel permeation chromatography. If the molecular weight is small, the compatibility with the vinyl polymer (I) is improved, the effect of self-adhesion becomes insufficient, and if the molecular weight is large, handling may be difficult due to high viscosity.

  The weight ratio (I) / (II) of the (meth) acrylic acid ester polymer (I) and the organic polymer (II) of the present invention is 99/1 to 70/30, but 99/1 to 80 / 20 is preferable, and 99/1 to 90/10 is more preferable. If the ratio of the organic polymer (II) is less than 1, it is not preferable because the compatibility is increased and the adhesiveness is lowered, and if it is more than 30, the miscibility is lowered and completely incompatible and the adhesiveness is decreased. Absent.

  The method for synthesizing the organic polymer (II) of the present invention is not particularly limited, and may be a free radical polymerization method or a controlled radical polymerization. However, from the viewpoint of various properties of the resulting curable composition, controlled radical polymerization is preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is more preferable.

<< Polyether polymer (III) having a crosslinkable silyl group >>
In the present invention, a polyether polymer (III) having a crosslinkable silyl group may be added.

  The polyether polymer having a crosslinkable silyl group will be described below.

<Main chain>
The main chain structure of the polyether polymer having a crosslinkable silyl group may be linear or branched, or a mixture thereof. Of these, a main chain derived from polyoxypropylene diol, polyoxypropylene triol or a mixture thereof is particularly preferable.
Examples of the main chain skeleton of the polyether polymer (III) having a crosslinkable silyl group include those having a repeating unit essentially represented by the general formula (30).

Formula (30):
-R ³⁰ -O- (30)
(Wherein R ³⁰ is a divalent alkylene group).

R ³⁰ in the general formula (30) is not particularly limited as long as it is a divalent alkylene group. Among them, an alkylene group having 1 to 14 carbon atoms is preferable, and a linear or branched chain having 2 to 4 carbon atoms. The alkylene group is more preferable. The repeating unit described in the general formula (5) is not particularly limited. For example, —CH ₂ O—, —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH (C ₂ H ₅ ) O—, —CH ₂ C (CH ₃ ) ₂ O—, —CH ₂ CH ₂ CH ₂ CH ₂ O— and the like, but polypropylene oxide comprising —CH ₂ CH (CH ₃ ) O— It is preferable that

  The above essential means that the above preferred repeating units are present in the polymer in an amount of 50% by weight or more, preferably 80% by weight or more.

  The main chain may or may not contain a urethane bond or urea bond.

  The number average molecular weight of the polyether-based polymer (III) having a crosslinkable silyl group is not particularly limited, but is preferably 5000 or more and more preferably in the range of 5000 to 50000 when measured by gel permeation chromatography. Preferably, it is more preferably in the range of 7000 to 25000, and most preferably in the range of 10000 to 20000.

  The molecular structure of the polyether-based polymer varies depending on the intended use and intended properties, and those described in JP-A-63-112642 can be used. Such polyoxyalkylenes can be obtained by conventional polymerization methods (anionic polymerization methods using caustic), cesium metal catalysts, JP-A 61-197631, JP-A 61-215622, JP-A 61-215623, and Porphyrin / aluminum complex catalysts exemplified in JP-A-61-218632 and the like, double metal cyanide complex catalysts exemplified in JP-B-46-27250 and JP-B-59-15336, etc., exemplified in JP-A-10-273512 It can be obtained by a method using a catalyst comprising a polyphosphazene salt.

  In a method using a porphyrin / aluminum complex catalyst, a double metal cyanide complex catalyst or a catalyst comprising a polyphosphazene salt, the molecular weight distribution (Mw / Mn) is 1.6 or less, and further a small value of oxy such as 1.5 or less. When an alkylene polymer can be obtained and the molecular weight distribution is small, there is an advantage that the viscosity of the composition can be reduced while maintaining the low modulus and high elongation of the cured product.

<Crosslinkable silyl group>
As the crosslinkable silyl group, the group represented by the above general formula (1) can be used as in the vinyl polymer, and the group represented by the above general formula (5) is preferable. The explanation about the group represented by the general formula (1) or the general formula (5) is similarly applied to the polyether polymer having a crosslinkable silyl group. The crosslinkable silyl group in the polyether polymer may have the same structure as the crosslinkable silyl group in the (meth) acrylic acid ester polymer having a crosslinkable silyl group, or may have a different structure.

  The bond between the crosslinkable silyl group and the polyether moiety is resistant to hydrolysis, so that there are at least three carbon atoms between the silicon atom of the silyl group and the ethyl oxygen atom of the polyether moiety. In addition, an alkylene group such as trimethylene and tetramethylene is preferable.

<Number and position of crosslinkable silyl groups>
The number of crosslinkable silyl groups is preferably more than 1.2 in view of the curability of the composition, more preferably 1.2 or more and 4.0 or less, and still more preferably 1.5. ~ 2.5 or less. Moreover, it is preferable that the crosslinkable silyl group of a polyether-type polymer exists in the terminal of a molecular chain from a viewpoint of the rubber elasticity of hardened | cured material, More preferably, it has a functional group in the both ends of a polymer.

  A polyether polymer having an average of less than 1.2 crosslinkable silyl groups can also be used. In this case, a cured product having high elongation at break, low bleeding, low surface contamination, and excellent paint adhesion can be obtained. Moreover, the viscosity of a composition can be reduced by setting the molecular weight of this polymer smaller. The lower limit of the number of crosslinkable silyl groups is preferably at least 0.1, more preferably 0.3 or more, and even more preferably 0.5 or more. The crosslinkable silyl group is preferably at the end of the molecular chain. Further, the crosslinkable silyl group of this polyether polymer is preferably only at one end in the main chain and not at the other end, but if it is 1.2 or less on average It is not particularly limited. In the case of reducing the viscosity by using a polyether polymer having an average of less than 1.2 crosslinkable silyl groups, the preferred molecular weight is less than 10,000, and further less than 5,000.

<Introduction method of crosslinkable silyl group>
The introduction of the crosslinkable silyl group may be performed by a known method. That is, for example, the following method can be mentioned. For example, in the case of an oxyalkylene polymer obtained using a double metal cyanide complex catalyst, JP-A-3-72527, and in the case of an oxyalkylene polymer obtained using a polyphosphazene salt and active hydrogen as a catalyst, JP-A-11-60723 is disclosed. It is described in.

  (1) An oxyalkylene polymer having a functional group such as a hydroxyl group at the terminal is reacted with an organic compound having an active group and an unsaturated group which are reactive with the functional group, or an unsaturated group-containing epoxy compound To obtain an unsaturated group-containing oxyalkylene polymer. Next, hydrosilylation is performed by allowing hydrosilane having a crosslinkable silyl group to act on the obtained reaction product.

  (2) An unsaturated group-containing oxyalkylene polymer obtained in the same manner as in the method (1) is reacted with a compound having a mercapto group and a crosslinkable silyl group.

(3) A functional group (hereinafter referred to as Y ′) having reactivity with this Y functional group to an oxyalkylene polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group (hereinafter referred to as Y functional group) at the terminal. And a compound having a crosslinkable silyl group).
Examples of the silicon compound having a Y ′ functional group include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, 3- Amino, 2-methylpropyltrimethoxysilane, N-ethyl-3-amino, 2-methylpropyltrimethoxysilane, 4-amino, 3-methylpropyltrimethoxysilane, 4-amino, 3-methylpropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and amino group-containing silanes such as partial Michael addition reaction products of various amino group-containing silanes with maleic esters and acrylate compounds; γ-mercaptopropyltrimethoxysilane Γ-mercaptopropylmethyl Mercapto group-containing silanes such as dimethoxysilane; epoxy-silanes such as γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; vinyltriethoxysilane, γ -Vinyl-type unsaturated group-containing silanes such as methacryloyloxypropyltrimethoxysilane and γ-acryloyloxypropylmethyldimethoxysilane; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; γ-isocyanatopropyl Isocyanate-containing silanes such as triethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltrimethoxysilane; methyldimethoxysilane, trimethoxysilane, methyldiethoxy Specific examples include hydrosilanes such as silane and triethoxysilane, but are not limited thereto.

  In addition, when producing a polymer having an average number of crosslinkable silyl groups of 1.2 or less, a polyether polymer having only one functional group in the molecule when introducing the crosslinkable silyl group. And a method for obtaining a polyether polymer having an average of 1.2 or less crosslinkable silyl groups by reacting the functional group with a compound having a crosslinkable silyl group in an equivalent amount or a smaller amount. By using a polyether polymer having an average of one or more functional groups in the molecule and reacting a compound having a crosslinkable silyl group that is less than the functional group, There is a method for obtaining a polyether polymer having an average of 1.2 or less.

<Amount of polyether polymer having a crosslinkable functional group>
The amount of the polyether polymer having a crosslinkable functional group may be any amount, but the weight ratio with respect to the (meth) acrylate polymer (I) having at least one crosslinkable silyl group. Is preferably in the range of 100/1 to 1/100, more preferably in the range of 100/5 to 5/100, and still more preferably in the range of 100/10 to 10/100. When the blend ratio of the (meth) acrylic acid ester polymer (I) is small, the weather resistance may be difficult to be exhibited.

<< Curable composition >>
The curable composition of the present invention includes, as components, a (meth) acrylic acid ester polymer (I) having at least one crosslinkable silyl group, and an organic polymer (II) having at least one crosslinkable silyl group. In addition, various additives such as the following can also be contained for the purpose of adjusting various physical properties and mechanical properties.

<Tin-based curing catalyst>
You may mix | blend a tin-type curing catalyst with the curable composition in this invention further. Examples of tin-based curing catalysts include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diisosulfate. Octyl malate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate, etc. Dialkyltin carboxylates;
Dialkyltin oxides such as dibutyltin oxide, dioctyltin oxide, a mixture of dibutyltin oxide and phthalate;
Reaction product of tetravalent tin compounds such as dialkyltin oxide and dialkyltin diacetate and low molecular weight silicon compounds having hydrolyzable silyl groups such as tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane and phenyltrimethoxysilane ;
Divalent tin compounds such as tin octylate, tin naphthenate and tin stearate;
Monoalkyltins such as monobutyltin compounds and monooctyltin compounds such as monobutyltin trisoctoate and monobutyltin triisopropoxide;
A reaction product and a mixture of an amine compound and an organic tin compound, such as a reaction product and a mixture of laurylamine and tin octylate;
Chelating compounds such as dibutyltin bisacetylacetonate, dioctyltin bisacetylacetonate, dibutyltin bisethylacetonate, dioctyltin bisethylacetonate;
Examples thereof include tin alcoholates such as dibutyltin dimethylate, dibutyltin diethylate, dioctyltin dimethylate, and dioctyltin diethylate.

  Among these, chelate compounds such as dibutyltin bisacetylacetonate and tin alcoholates are more preferable because of their high activity as silanol condensation catalysts. Further, dibutyltin dilaurate is preferable because the final curable composition is less colored, low in cost, and easily available.

These tin-based curing catalysts may be used alone or in combination of two or more.
The blending amount of the tin-based curing catalyst is preferably about 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylic ester polymer (I) and the organic polymer (II). More preferably, it is 5 to 10 parts by weight. If the amount of the tin-based curing catalyst is less than this range, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, when the blending amount of the tin-based curing condensation catalyst exceeds this range, local heat generation or foaming occurs during curing, making it difficult to obtain a good cured product, shortening the pot life, and reducing workability. It tends to be easy.

<Other curing catalysts>
The polymer having a crosslinkable silyl group is crosslinked and cured by forming a siloxane bond in the presence or absence of various conventionally known condensation catalysts. The properties of the cured product can be broadly created from rubbery to resinous depending on the molecular weight and main chain skeleton of the polymer.

  As such a condensation catalyst, in addition to the above-described tin-based curing catalyst, the following can also be used. Titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; Organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate and titanium tetraacetylacetate Chelate compounds such as nate; lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, Xylylenediamine, triethylenediamine, guanidine, diphenylgua Gin, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) Amine compounds such as these, or salts of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines and epoxy compounds; Silanol condensation catalysts such as silane coupling agents having amino groups such as aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; and other acidic catalysts, basic catalysts, etc. Examples of such known silanol condensation catalysts.

  These catalysts may be used alone or in combination of two or more, or may be used in combination with a tin-based curing catalyst. The blending amount of the condensation catalyst is preferably about 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylic ester polymer (I) and the organic polymer (II). 5-10 weight part is still more preferable. If the amount of the silanol condensation catalyst is less than this range, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, if the blending amount of the silanol condensation catalyst exceeds this range, local heat generation and foaming occur during curing, and it becomes difficult to obtain a good cured product, and the pot life becomes too short, which is preferable from the viewpoint of workability. Absent.

In the curable composition of the present invention, in order to further increase the activity of the condensation catalyst, the general formula (19)
R ²⁵ _c Si (OR ²⁶ ) _4-c (19)
(In the formula, R ²⁵ and R ²⁶ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. When two or more R ²⁵ or R ²⁶ are present, they are It may be the same or different, and c is any of 0, 1, 2, and 3), and a silicon compound having no silanol group may be added.

Examples of the silicon compound include, but are not limited to, R ^{25 in} the general formula (18) such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and triphenylmethoxysilane. Is preferably an aryl group having 6 to 20 carbon atoms because it has a large effect of accelerating the curing reaction of the composition. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are most preferable because of low cost and easy availability.

  The compounding amount of the silicon compound is preferably about 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylic acid ester polymer (I) and the organic polymer (II). 1-10 weight part is still more preferable. When the compounding amount of the silicon compound is below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, when the compounding amount of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease.

<Adhesive agent>
A silane coupling agent or an adhesion-imparting agent other than the silane coupling agent can be added to the composition of the present invention. When the adhesion-imparting agent is added, the joint width or the like varies due to an external force, thereby further reducing the risk of the sealing material peeling from the adherend such as a siding board. Further, in some cases, it is not necessary to use a primer used for improving adhesion, and simplification of construction work is expected. Specific examples of the silane coupling agent include isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane Amino groups such as silane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane -Containing silanes; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane and other mercapto group-containing silanes; γ-glycidoxypropyl Trimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Epoxy group-containing silanes such as ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N- (β-carboxymethyl) aminoethyl-γ-aminopropyl Carboxysilanes such as trimethoxysilane; Vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acryloyloxypropylmethyltriethoxysilane; γ -Halogen-containing silanes such as chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. .

  The silane coupling agent is preferably used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylic acid ester polymer (I) and the organic polymer (II). More preferably, it is used in the range of 0.5 to 10 parts by weight. The effects of the silane coupling agent added to the curable composition of the present invention are various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, When used on organic substrates such as polyethylene, polypropylene, polycarbonate, etc., it exhibits a significant adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable.

  Specific examples other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates.

  The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved. Although not particularly limited, 0.1-20 parts by weight of a silane coupling agent is used in combination with the above-mentioned adhesion-imparting agent in order to improve adhesion, particularly adhesion to a metal-coated surface such as an oil pan. Is preferred.

<Plasticizer>
You may use various plasticizers for the curable composition of this invention as needed. When a plasticizer is used in combination with a filler to be described later, it becomes more advantageous because the elongation of the cured product can be increased or a large amount of filler can be mixed, but it is not necessarily added. Although it does not specifically limit as a plasticizer, For purposes, such as adjustment of physical properties and adjustment of properties, for example, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate Non-aromatic dibasic esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetylricinoleate; diethylene glycol dibenzoate, triethylene glycol dibenzoate Polyalkylene glycol esters such as pentaerythritol ester; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Polystyrenes such as α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyethylene Polyether polyols such as glycol, polypropylene glycol, polytetramethylene glycol and the like, and polyethers such as derivatives obtained by converting hydroxyl groups of these polyether polyols to ester groups, ether groups, etc .; epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acids Epoxy plasticizers such as esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, di- (2-ethylhexyl) 4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate. Of these, E-PS is particularly preferred. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Polyester-based plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; acrylic plastics Examples thereof include vinyl polymers obtained by polymerizing vinyl monomers including an agent by various methods.

  Among them, the polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15000 is added, whereby the viscosity and slump property of the curable composition and the tensile strength of the cured product obtained by curing the composition, Mechanical properties such as elongation can be adjusted, and initial physical properties can be maintained over a long period of time as compared to the case of using a low molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule. In addition, when used outdoors, bleeding to the surface layer of the plasticizer is suppressed and dust and the like are less likely to adhere, and also when applying paint etc. on the surface of the curable composition, As a result, the coating film is less likely to become dirty, and the appearance can be maintained for a long time. Although not limited, the polymer plasticizer may or may not have a functional group.

  Although the number average molecular weight of the polymer plasticizer was described as 500-15000 above, Preferably it is 800-10000, More preferably, it is 1000-8000. If the molecular weight is too low, the plasticizer may flow out over time due to heat or rain, and the initial physical properties may not be maintained for a long time. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen.

  Among these polymer plasticizers, those compatible with the (meth) acrylic acid ester polymer (I) are preferable. Examples of the method for synthesizing the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers. The latter acrylic plasticizer is prepared by a high temperature continuous polymerization method (USP 4414370, JP 59-6207, JP-B-5-58005, JP 1-313522, USP 5010166) without using a solvent or a chain transfer agent. More preferred for the purposes of the present invention. Examples thereof include, but are not limited to, ARUFON UP-1000, UP-1020, UP-1110, etc. manufactured by Toagosei Co., Ltd., JDX-P1000, JDX-P1010, JDX-P1020, etc. manufactured by Johnson Polymer Co., Ltd. . Of course, the living radical polymerization method can also be mentioned as another synthesis method. According to this method, the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable, but it is not limited thereto.

  The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.8. 1.7 or less is more preferable, 1.6 or less is still more preferable, 1.5 or less is more preferable, 1.4 or less is especially preferable, and 1.3 or less is the most preferable.

  The plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more, but is not necessarily required. Further, if necessary, a high molecular plasticizer may be used, and a low molecular plasticizer may be further used in a range that does not adversely affect the physical properties.

  These plasticizers can also be blended at the time of polymer production.

  The amount of the plasticizer used is not limited, but is preferably 5 to 800 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylic acid ester polymer (I) and the organic polymer (II). More preferably, it is 10-600 weight part, More preferably, it is 10-500 weight part. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 800 parts by weight, the mechanical strength of the cured product may be insufficient.

<Filler>
You may use various fillers for the curable composition of this invention as needed. The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, mica, walnut shell powder, rice husk powder, graphite, white clay, silica (fumed silica, precipitated silica, crystalline silica, fused silica) , Dolomite, anhydrous silicic acid, hydrous silicic acid, etc.), reinforcing filler such as carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, Fillers such as organic bentonite, ferric oxide, red pepper, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate and shirasu balloon; asbestos, glass fiber and glass filament, carbon fiber, Examples include fibrous fillers such as Kevlar fiber and polyethylene fiber. .

  Of these fillers, precipitated silica, fumed silica, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable.

In particular, when you want to obtain a cured product with high strength with these fillers, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, crystalline silica, molten A filler selected from silica, calcined clay, clay and activated zinc white can be added. Among them, the specific surface area (according to BET adsorption method) of 50 m ² / g or more, usually 50 to 400 m ² / g, is preferably 100 to 300 m ² / g approximately ultrafine powdery silica preferred. Further, silica whose surface has been previously hydrophobically treated with an organosilicon compound such as organosilane, organosilazane, diorganopolysiloxane, etc. is more preferred.

  A more specific example of the silica-based filler having a high reinforcing property is not particularly limited, but is one of combustion method silica (fumed silica) Aerosil of Nippon Aerosil Co., Ltd. and precipitation method silica. Nipsil manufactured by Nippon Silica Co., Ltd. Particularly for fumed silica, it is more preferable to use fumed silica having an average primary particle diameter of 5 nm to 50 nm because the reinforcing effect is particularly high.

  In addition, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient. The larger the specific surface area value, the greater the effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product.

  Furthermore, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent. When the surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved as compared with the case where calcium carbonate that is not surface-treated is used, and the adhesiveness and weather resistance of the curable composition are improved. The improvement effect is considered to be further improved. As the surface treatment agent, organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents are used. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc. And salts of these fatty acids such as sodium and potassium, and alkyl esters of these fatty acids. Specific examples of the surfactants include polyoxyethylene alkyl ether sulfates and long chain alcohol sulfates, sulfate anion surfactants such as sodium salts and potassium salts thereof, alkylbenzene sulfonic acids, and alkylnaphthalenes. Examples thereof include sulfonic acid, paraffin sulfonic acid, α-olefin sulfonic acid, alkyl sulfone succinic acid and the like, and sulfonic acid type anionic surfactants such as sodium salt and potassium salt thereof. The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight and more preferably in the range of 1 to 5% by weight with respect to calcium carbonate. When the treatment amount is less than 0.1% by weight, the workability, adhesiveness and weatherability may not be sufficiently improved. When the treatment amount exceeds 20% by weight, the storage stability of the curable composition may be reduced. May decrease.

  Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is used when particularly improving effects such as thixotropy of the compound, breaking strength of the cured product, elongation at break, adhesion and weather resistance are expected. Is preferred.

  On the other hand, heavy calcium carbonate may be added for the purpose of lowering the viscosity of the compound, increasing the amount, reducing costs, etc. When using this heavy calcium carbonate, use the following as necessary. be able to.

Heavy calcium carbonate is obtained by mechanically pulverizing and processing natural chalk (chalk), marble, limestone, and the like. There are dry and wet methods for the pulverization method, but wet pulverized products are often not preferred because they often deteriorate the storage stability of the curable composition of the present invention. Heavy calcium carbonate becomes products having various average particle sizes by classification. Although not particularly limited, when the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product is expected, the specific surface area has a value of 1.5 m ² / g or more and 50 m ² / g or less. , more preferably from 2m ² / g or more 50 m ² / g or less, more preferably 2.4 m ² / g or more ^{50m 2 / g, 3m 2 /} g or more 50 m ² / g or less is particularly preferred. When the specific surface area is less than 1.5 m ² / g, the improvement effect may not be sufficient. Of course, this is not the case when the viscosity is simply reduced or when the purpose is only to increase the viscosity.

  In addition, the value of the specific surface area means a measurement value by an air permeation method (a method for obtaining a specific surface area from air permeability with respect to a powder packed bed) performed according to JIS K 5101 as a measurement method. As a measuring instrument, it is preferable to use a specific surface area meter SS-100 manufactured by Shimadzu Corporation.

These fillers may be used alone or in combination of two or more according to the purpose and necessity. Although there is no particular limitation, for example, if a combination of heavy calcium carbonate and colloidal calcium carbonate having a specific surface area value of 1.5 m ² / g or more as necessary, the increase in the viscosity of the compound is moderately suppressed, and the cured product The effect of improving the breaking strength, breaking elongation, adhesiveness and weathering adhesion can be greatly expected.

  When the filler is used, the addition amount is 5 to 5000 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylate polymer (I) and the organic polymer (II). It is preferably used, more preferably 10 to 2500 parts by weight, and particularly preferably 15 to 1500 parts by weight. When the blending amount is less than 5 parts by weight, the effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product may not be sufficient. May decrease. A filler may be used independently and may be used together 2 or more types.

<Micro hollow particles>
Furthermore, for the purpose of reducing the weight and cost without causing a significant decrease in physical properties, fine hollow particles may be used in combination with these reinforcing fillers.

Such fine hollow particles (hereinafter referred to as balloons) are not particularly limited, but have a diameter of 1 mm or less, preferably 500 μm or less, and more preferably, as described in “The latest technology of functional filler” (CMC). Is a hollow body made of an inorganic or organic material of 200 μm or less. In particular, it is preferable to use a micro hollow body having a true specific gravity of 1.0 g / cm ³ or less, and it is more preferable to use a micro hollow body having a specific gravity of 0.5 g / cm ³ or less.

  Examples of the inorganic balloons include silicate balloons and non-silicate balloons, silicate balloons include shirasu balloons, perlite, glass balloons, silica balloons, fly ash balloons, etc., and non-silicate balloons include alumina. Examples include balloons, zirconia balloons, and carbon balloons. As specific examples of these inorganic balloons, as a white balloon, Idichi Kasei Winlight, Sanki Kogyo Sankilite, as a glass balloon, Sumitomo 3M Cell Star Z-28, EMERSON & CURING manufactured by MICRO BALLON, PITTSBURGE CORNING CELAMIC GLASSMODULES, 3M GLASS BUBBLES, Q-CEL made by Asahi Glass as a silica balloon, E-SPHERES made by Taiheiyo Cement, CERAOSHERES made by PFAMARKETING, FILLITE U. S. FILLITE manufactured by A, BW manufactured by Showa Denko as an alumina balloon, HOLLOW ZIRCONIUM SPHEES manufactured by ZIRCOA as a zirconia balloon, and Kureha sphere made by Kureha Chemical, and a carbo sphere manufactured by GENERAL TECHNOLOGIES as a carbon balloon are commercially available.

  Examples of the organic balloon include a thermosetting resin balloon and a thermoplastic resin balloon. The thermosetting balloon includes a phenol balloon, an epoxy balloon, and a urea balloon. The thermoplastic balloon includes a saran balloon, a polystyrene balloon, Examples thereof include polymethacrylate balloons, polyvinyl alcohol balloons, and styrene-acrylic balloons. A crosslinked thermoplastic balloon can also be used. The balloon here may be a balloon after foaming, or a balloon containing a foaming agent may be foamed after blending.

  Specific examples of these organic balloons include UCAR and PHENOLIC MICROBALLONONS made by Union Carbide as phenolic balloons, ECCOSPHERES made by EMERSON & CUMING as epoxy balloons, ECCOSPHERES VF-O made by EMERSON & CUMING, and DOWEMIC PHALS made by Saran Balloon by Saran Balloon. , EXPANSEL made by AKZO NOBEL, Matsumoto Microsphere made by Matsumoto Yushi Seiyaku, DYLITE EXPANDABLE POLYSTYRENE made by ARCO POLYMERS as polystyrene balloon, EXPANDABLE POLYSTENERENE made by BASF WYANDOTE , Crosslinked styrene - SX863 is acrylic acid balloon made by Japan Synthetic Rubber (P) are commercially available.

  The balloons may be used alone or in combination of two or more. In order to improve the dispersibility and the workability of the compound by using fatty acid, fatty acid ester, rosin, rosin lignin, silane coupling agent, titanium coupling agent, aluminum coupling agent, polypropylene glycol, etc. on the surface of these balloons. The processed one can also be used. These balloons are used for weight reduction and cost reduction without impairing flexibility and elongation / strength among physical properties when the compound is cured.

  The content of the balloon is not particularly limited, but is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylic acid ester polymer (I) and the organic polymer (II). Preferably it can be used in the range of 0.1 to 30 parts by weight. If this amount is less than 0.1 parts by weight, the effect of weight reduction is small, and if it is 50 parts by weight or more, a decrease in tensile strength may be observed among the mechanical properties when this compound is cured. When the specific gravity of the balloon is 0.1 or more, 3 to 50 parts by weight, more preferably 5 to 30 parts by weight is preferable.

<Physical property modifier>
You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention.

  Although it does not specifically limit as a physical property regulator, For example, alkyl alkoxysilanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxy Alkoxysilanes having a functional group such as a silane; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, the hardness when the composition of the present invention is cured can be increased, the hardness can be decreased, and the elongation can be increased. The said physical property modifier may be used independently and may be used together 2 or more types.

  The physical property modifier is not particularly limited, but is preferably 0.1 to 80 parts by weight, more preferably 100 parts by weight based on the total amount of the (meth) acrylic acid ester polymer (I) and the organic polymer (II). Can be used in the range of 0.1 to 50 parts by weight. If this amount is less than 0.1 parts by weight, the effect of weight reduction is small, and if it is 80 parts by weight or more, a decrease in tensile strength may be observed among the mechanical properties when this compound is cured.

<Thixotropic agent (anti-sagging agent)>
A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability.

  The sagging preventing agent is not particularly limited, and examples thereof include polyamide waxes, hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more.

  The thixotropic agent is 0.1 to 50 parts by weight, preferably 0.2 to 25 parts per 100 parts by weight of the total amount of the (meth) acrylic acid ester polymer (I) and the organic polymer (II). Part by weight can be added. If the addition amount is less than 0.1 parts by weight, the thixotropy imparting effect is not sufficiently exhibited, and if it is used in excess of 50 parts by weight, the viscosity of the formulation is increased and the storage stability of the formulation is further reduced.

<Photo-curing substance>
You may add a photocurable substance to the curable composition of this invention as needed. A photo-curing substance is a substance that undergoes a chemical change in the molecular structure in a short period of time due to the action of light, resulting in a change in physical properties such as curing. By adding this photocurable substance, the adhesiveness (also referred to as residual tack) of the cured product surface when the curable composition is cured can be reduced. This photo-curable substance is a substance that can be cured by exposure to light, but a typical photo-curable substance is allowed to stand at room temperature for one day, for example, in an indoor location where the sun is exposed (near the window). It is a substance that can be cured by. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and the type thereof is not particularly limited. For example, unsaturated acrylic compounds, polycinnamic acid Examples thereof include vinyls and azido resins.

  Specific examples of unsaturated acrylic compounds include (meth) acrylic acid esters of low molecular weight alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and neopentyl alcohol; bisphenol A, isocyanuric acid, and the like. (Meth) acrylic acid esters of alcohols obtained by modifying acids or the above low molecular weight alcohols with ethylene oxide or propylene oxide; polyether polyols having a main chain as a polyether and having a hydroxyl group at the terminal, in a polyol having a main chain as a polyether A polymer polyol obtained by radical polymerization of a vinyl monomer, a polyester polyol having a main chain of polyester and a hydroxyl group at the terminal, a main chain of a vinyl or (meth) acrylic polymer, and a hydroxyl group in the main chain (Meth) acrylic acid esters such as polyols having epoxy; epoxy acrylate oligomers obtained by reacting bisphenol A type or novolak type epoxy resins with (meth) acrylic acid; containing polyols, polyisocyanates and hydroxyl groups ( Examples thereof include urethane acrylate oligomers having a urethane bond and a (meth) acryl group in a molecular chain obtained by reacting meth) acrylate or the like.

  Polyvinyl cinnamate is a photosensitive resin having a cinnamoyl group as a photosensitive group, and includes many polyvinyl cinnamate derivatives other than those obtained by esterifying polyvinyl alcohol with cinnamic acid.

  Azide resin is known as a photosensitive resin having an azide group as a photosensitive group. In general, in addition to a rubber photosensitive solution in which an azide compound is added as a photosensitive agent, “photosensitive resin” (published March 17, 1972). , Published by the Printing Society Press, page 93 to page 106 to page 117), these are detailed examples, and these can be used alone or in combination, and a sensitizer can be added if necessary.

  Among the above-mentioned photocurable materials, unsaturated acrylic compounds are preferable because they are easy to handle.

  The photocurable substance is preferably added in an amount of 0.01 to 30 parts by weight based on 100 parts by weight of the total amount of the (meth) acrylic acid ester polymer (I) and the organic polymer (II). If the amount is less than 0.01 parts by weight, the effect is small, and if it exceeds 30 parts by weight, the physical properties may be adversely affected. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.

<Air oxidation curable substance>
If necessary, an air oxidation curable material may be added to the curable composition of the present invention. The air oxidation curable substance is a compound having an unsaturated group that can be crosslinked and cured by oxygen in the air. By adding this air oxidation curable substance, the tackiness (also referred to as residual tack) of the cured product surface when the curable composition is cured can be reduced. The air oxidation curable substance in the present invention is a substance that can be cured by contact with air, and more specifically, has a property of curing by reacting with oxygen in the air. A typical air oxidation curable substance can be cured by, for example, standing in air indoors for 1 day.

  Examples of the air oxidative curable substance include drying oils such as paulownia oil and linseed oil; various alkyd resins obtained by modifying these drying oils; acrylic polymers, epoxy resins and silicone resins modified with drying oils; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers and copolymers, and various modified products of the polymers and copolymers (maleinized modified products, boiled oil modified products, etc.) Is given as a specific example. Of these, paulownia oil, diene polymer liquid (liquid diene polymer) and modified products thereof are particularly preferred.

  Specific examples of the liquid diene polymer include a liquid polymer obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene, and copolymerizable with these diene compounds. Polymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene having a main component with a diene compound, and various modified products thereof (maleinized modified products, boiled oils) Modified products, etc.). These may be used alone or in combination of two or more. Of these liquid diene compounds, liquid polybutadiene is preferred.

  The air oxidation curable substance may be used alone or in combination of two or more. In addition, the effect may be enhanced if a catalyst that promotes the oxidative curing reaction or a metal dryer is used together with the air oxidative curable substance. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate, amine compounds, and the like.

  The air oxidation curable substance is preferably added in an amount of 0.01 to 30 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylic acid ester polymer (I) and the organic polymer (II). If the amount is less than 0.01 parts by weight, the effect is small, and if it exceeds 30 parts by weight, the physical properties may be adversely affected.

<Antioxidant, light stabilizer>
In the curable composition of the present invention, an antioxidant or a light stabilizer may be used as necessary. Various types of antioxidants and light stabilizers are known. For example, “Antioxidant Handbook” issued by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242) issued by CMC Although various things described in the above etc. are mentioned, it is not necessarily limited to these.

  Antioxidants are not particularly limited, but thioether antioxidants such as ADK STAB PEP-36 and ADK STAB AO-23 (all manufactured by Asahi Denka Kogyo), Irgafos 38, Irgafos 168, Irgafos P-EPQ (all above Phosphorous antioxidants such as Specialty Chemicals); hindered phenolic antioxidants and the like. Of these, hindered phenol compounds as shown below are preferred.

Specific examples of the hindered phenol compound include the following.
2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di- or tri) (α-methylbenzyl) phenol, 2,2′-methylenebis (4 ethyl-6-t-butylphenol), 2,2'-methylenebis (4methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4 ' -Thiobis (3-methyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, triethylene glycol-bis- [3- (3-t- Butyl-5-methyl-4hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl -3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4- Hide Xylbenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate) calcium, tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4 -Bis [(octylthio) methyl] o-cresol, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t -Butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydro Xylphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxy) Phenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) -benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4 -Hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid Bis (1,2,2,6,6-pentamethyl-4-piperidyl), 2,4-di-t-butylphenyl-3,5-di Like t- butyl-4-hydroxy benzoate.

  In terms of product names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above Manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.), ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-616, ADK STAB AO-635, ADK STAB AO-658, ADK STAB AO-80, ADK STAB AO-15, ADK STAB AO-18, ADK STAB 328, ADK STAB AO-37 (all manufactured by Asahi Denka Kogyo), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1 10, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all of which are manufactured by Ciba Specialty Chemicals), Sumizer GM, and Sumilizer GA-80 (All of these are manufactured by Sumitomo Chemical Co., Ltd.) and the like, but are not limited thereto.

  Examples of the light stabilizer include benzotriazole compounds such as Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, Tinuvin 213 (all of which are manufactured by Ciba Specialty Chemicals) and Tinuvin 1577. UV absorbers such as triazine-based compounds such as benzophenone-based compounds such as CHIMASSORB 81, benzoate-based compounds such as Tinuvin 120 (manufactured by Ciba Specialty Chemicals), and hindered amine compounds.

Of these, hindered amine compounds are more preferred. Specific examples of the hindered amine compound include, but are not limited to, the following.
Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of succinate, poly [{6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (3aminopropyl) ethylenediamine- 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate, succinic acid bis (2,2,6,6-tetramethyl-4-piperidinyl) ester, and the like.

  In terms of product names, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by Ciba Specialty Chemicals), ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA -63, ADK STAB LA-68, ADK STAB LA-82, ADK STAB LA-87 (all manufactured by Asahi Denka Kogyo), SANOL LS-770, SANOL LS-765, SANOL LS-2926, SANOL LS-2626, SANOL LS- 1114, Sanol LS-744, Sanol LS-440 (all of which are manufactured by Sankyo) and the like can be exemplified, but the invention is not limited thereto.

  Antioxidants and light stabilizers may be used in combination, and are particularly preferred because they can further exert their effects and improve heat resistance, weather resistance, and the like. Tinuvin C353, Tinuvin B75 (both manufactured by Ciba Specialty Chemicals) and the like in which an antioxidant and a light stabilizer are mixed in advance may be used.

  In addition, in order to improve weather resistance, there are cases where a UV absorber and a hindered amine compound (HALS) are combined, but since this combination may be more effective, it is not particularly limited but may be used in combination. It may be preferable to use together.

  The antioxidant or light stabilizer is not particularly limited, but it is more preferable to use a high molecular weight one because the effect of improving the heat resistance of the present invention is exhibited over a longer period of time.

  The amount of the antioxidant or light stabilizer used is 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylic acid ester polymer (I) and the organic polymer (II), respectively. It is preferable that it is the range of these. If the amount is less than 0.1 part by weight, the effect of improving the heat resistance is small, and if it exceeds 20 parts by weight, the effect is not greatly different, which is economically disadvantageous.

Other Additives Various additives may be added to the curable composition of the present invention as needed for the purpose of adjusting the physical properties of the curable composition or the cured product. Examples of such additives include, for example, flame retardants, curability modifiers, anti-aging agents, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments And foaming agents. These various additives may be used alone or in combination of two or more.

  Specific examples of such additives are described in, for example, the specifications of JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, and JP-A-64-22904. Yes.

<Preparation of curable composition>
The curable composition of the present invention may be prepared as a one-component type in which all the components are pre-blended and stored in a sealed state and cured by moisture in the air after construction. Components such as an agent and water may be blended and adjusted as a two-component type in which the blending material and the polymer composition are mixed before use. The one-component type is preferable because it is not only easy to use but also has a low possibility of causing insufficient curing due to poor mixing of the curing catalyst in the two-component type. When the two-component type is used, a colorant can be added when the two components are mixed. For example, when providing a sealing material that matches the color of the siding board, an abundant color alignment is possible with a limited stock. This makes it easy to cope with the increase in the number of colors requested from the market, and is preferable for low-rise buildings. The colorant is easy to work if, for example, a pigment and a plasticizer, and in some cases, a paste prepared by mixing a filler is used. Further, by adding a retarder during mixing of the two components, the curing rate can be finely adjusted at the work site.

<< Usage >>
The curable composition of the present invention includes, but is not limited to, a highly durable building elastic sealant used for working joints, a siding board sealant, a double glazing sealant, a vehicle sealant, etc. And industrial sealing materials, electrical and electronic component materials such as solar cell backside sealants, electrical insulation materials such as insulation coatings for electric wires and cables, adhesives, adhesives, elastic adhesives, contact adhesives, tiles Adhesives, reactive hot melt adhesives, paints, powder paints, coating materials, foams, sealing materials for can lids, potting agents for electrical and electronic equipment, films, gaskets, casting materials, various molding materials, artificial marble , And anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cutting parts), and vibration / vibration / soundproofing used in automobiles, ships, home appliances, etc. Seismic isolation materials, automobile parts, electrical parts, various machine parts liquid sealing agent used in such, are available in a variety of applications such as waterproofing agents.

  Furthermore, the molded product showing rubber elasticity obtained from the curable composition of the present invention can be widely used mainly for gaskets and packings. For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. As engine parts, they can be used for hoses for cooling, fuel supply, exhaust control, etc., sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts. In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake cans, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube, Speaker gaskets, speaker edges, turntables for acoustic equipment such as diaphragm valves and air pipes Seat, belts, pulleys, and the like. In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like. In the sports field, it can be used for all-weather pavement materials, gymnasium floors, etc. as sports floors, shoe sole materials, midsole materials, etc. as sports shoes, golf balls etc. as ball for ball games. In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like. In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, etc. Can be used for draging hoses, oil skimmers, etc. In addition, it can be used for sheet rubber, mats, foam boards and the like.

  Among these, the curable composition of the present invention is particularly useful as a sealing material and an adhesive, and is particularly useful for applications requiring weather resistance and durability and for applications requiring transparency. Moreover, since the curable composition of this invention is excellent in a weather resistance and adhesiveness, it can be used for the construction method of an outer wall tile adhesion | attachment without joint filling. Furthermore, it can be used for adhesion of materials with different linear expansion coefficients, application of elastic adhesives for adhesion of members that are repeatedly displaced by heat cycle, and coating agents for applications where the base can be seen by taking advantage of transparency. It is also useful for applications such as adhesives used for bonding transparent materials such as glass, polycarbonate and methacrylic resin.

<< Method for improving adhesion >>
In the curable composition containing the (meth) acrylic acid ester polymer (I) having a crosslinkable silyl group, the present invention is used in combination with an organic polymer (II) whose solubility parameter is 0.2 or more larger than (I). A method for improving adhesion to a substrate. In particular, it is effective for improving the adhesion to difficult-to-adhere substrates such as high temperature baking fluorinated aluminum substrates and acrylic substrates. In order to improve the adhesion to the substrate, various types of adhesion imparting agents are commercially available. However, those containing a solvent deteriorate the working environment, and sila coupling agents are generally expensive. Therefore, there is a problem that it is difficult to use a large amount. The organic polymer (II) of the present invention does not have the above problems and can be used in a wide range of applications.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples.

  In the following examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.

(Production Examples 1-4)
Table 1 shows the amount of each raw material used (parts by weight).

Synthesis of alkenyl group-terminated (meth) acrylic acid ester polymer Acrylic acid ester (described as initial charge in Table 1), cuprous bromide, acetonitrile (described as acetonitrile for polymerization in Table 1) under a nitrogen stream, Diethyl 2,5-dibromoadipate was charged and stirred at 80 ° C. To this was added pentamethyldiethylenetriamine (hereinafter referred to as triamine) to initiate the reaction. In the middle, the remaining acrylic acid ester (shown as additional in Table 1) was intermittently added, and the stirring of the reaction solution was continued so that the temperature of the reaction solution became 80 ° C to 90 ° C while adding triamine as appropriate. After the reaction rate of the acrylic ester reached 95%, the pressure in the reaction vessel was reduced to remove volatile components.

  Acetonitrile (described in Table 1 as acetonitrile for diene reaction) and 1,7-octadiene were added thereto, triamine was further added, and the mixture was heated and stirred at 80 ° C. Thereafter, the pressure inside the reaction vessel was reduced to remove volatile components.

  This was diluted with butyl acetate, synthetic hydrotalcite, aluminum silicate, and filter aid were added, and the mixture was heated and stirred in an oxygen / nitrogen mixed gas atmosphere. After removing solids, the solution was concentrated. Synthetic hydrotalcite and aluminum silicate were added, and the mixture was heated and stirred under reduced pressure. This was diluted with butyl acetate, further added with synthetic hydrotalcite and aluminum silicate and stirred with heating. After removing the solid content, the solution was concentrated to obtain an alkenyl-terminated (meth) acrylic acid ester polymer.

Synthesis of silyl group-terminated (meth) acrylic acid ester polymer (meth) acrylic acid ester polymer having an alkenyl group obtained by the above method, dimethoxymethylsilane (hereinafter referred to as DMS: 2.0 for alkenyl group) Molar equivalent), methyl orthoformate (1.0 molar equivalent with respect to the alkenyl group), platinum catalyst [bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst in isopropanol solution : Hereinafter referred to as platinum catalyst] (10 mg as platinum relative to 1 kg of polymer) was mixed and heated and stirred at 100 ° C. in a nitrogen atmosphere. After heating and stirring for about 1 hour, volatile components such as unreacted DMS were distilled off under reduced pressure to obtain a (meth) acrylic acid ester polymer having dimethoxysilyl groups at both ends.

  The number of silyl groups introduced per molecule of the obtained (meth) acrylic acid ester polymer, molecular weight, molecular weight distribution, and solubility parameter (SP) are also shown in Table 1.

(Production Examples 5 and 6)
Table 2 shows the amount of each raw material used (parts by weight).

Synthesizing the organic polymer having a silyl group, a thermometer, a reflux condenser, a nitrogen gas inlet tube, and a reactor equipped with a dropping funnel were charged with component (a) in Table 2 while introducing nitrogen gas. After the temperature was raised to ° C., the mixture of the components (a) in Table 1 was added dropwise at a constant rate over 5 hours from the dropping funnel. Next, the mixed solution of the component (c) was dropped at a constant rate over 1 hour. Then, after stirring at 110 degreeC for 2 hours continuously, it cooled to room temperature. Finally, component (D) in Table 1 was added and stirred to obtain an organic polymer.

  Table 2 shows the number average molecular weight and solubility parameter (SP) measured by GPC of the obtained organic polymer.

(Production Example 7)
Synthesis of unsaturated group-terminated polypropylene oxide 0.026 parts of zinc hexacyanocobaltate-glyme complex, 1.3 parts of THF solution of dipropylene glycol and 6.2 parts of propylene oxide were added to an autoclave at 76 ° C. in a nitrogen atmosphere. Reacted. Thereafter, 93.8 parts of propylene oxide was added to the reaction system. Unreacted monomer and solvent were collected and purified to obtain an oily polymer.
To 100 parts of the polymer obtained above, 4.8 parts of a methanol solution of sodium methoxide (28 wt%) was added and reacted at 130 ° C. for 1 hour in an autoclave, and then devolatilized under reduced pressure. It returned to nitrogen atmosphere, 2.3 parts of allyl chloride was added, and it was made to react for 2 hours.
This reaction mixture was dissolved in hexane, adsorbed with aluminum silicate, and then hexane was distilled off under reduced pressure to obtain unsaturated group-terminated polypropylene oxide.

Synthesis of crosslinkable silyl group- terminated polypropylene oxide 100 parts of unsaturated group-terminated polypropylene oxide obtained in the above synthesis was charged into a pressure-resistant glass reaction vessel, and an isopropanol solution of chloroplatinic acid (25 g of H ₂ PtCl ₆ · 6H ₂ O Was dissolved in 500 g of isopropanol) and 0.016 part was added, followed by stirring for 30 minutes. 1.75 parts of methyldimethoxysilane was added dropwise and reacted at 90 ° C. for 2 hours. Volatile components were removed by reducing the pressure, and silyl group-terminated polypropylene oxide was obtained. The polymer had a viscosity of 6 Pa · s, a number average molecular weight of 17,300, and a molecular weight distribution of 1.14.

(Calculation method of solubility parameter (SP value))
Solubility parameter (SP value) is measured in Polym. Eng. Sci. (Polymer Engineering Science), 14 (2), 147 (1974). F. It is obtained from the Fedors equation. Specifically, the solubility parameter (SP) of the structural unit based on each monomer constituting the (meth) acrylic polymer is a value defined by the following formula (1), and is a substance depending on temperature. It is an inherent constant.
Solubility parameter (SP value) = (ΔE / V) ^1/2 (20)
(However, ΔE: molecular cohesive energy, V: molecular volume.)
The SP value of the structural unit based on each monomer is a structure in which the monomer is polymerized and exists in the polymer chain, that is, if the vinyl monomer is used, the double bond is opened. As a structure having a single bond, R.I. F. This is calculated from ΔE, V in the Fedors equation and corresponds to the SP value of the homopolymer of the monomer.
Further, the solubility parameter of the (meth) acrylic polymer is such that the molar fraction ni (ni is a molecular weight) in the polymer of the i-th monomer Mi (i is an integer of 1 to n) constituting the polymer. From the molar fraction of the monomer Mi (the meaning of the suffix [i] is the same as described above) and the solubility parameter (SPi) of the structural unit based on the monomer, the following formula ( 21).
Solubility parameter (SP value) = Σ (SPi × ni) (21)

(Examples 1 to 8, Comparative Examples 1 to 4)
Polymers obtained in Production Examples 1 to 7, surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Shiraka Hana CCR-B), heavy calcium carbonate (manufactured by Shiroishi Calcium Co., Ltd., trade name: White) SB), plasticizer (manufactured by Kyowa Hakko Co., Ltd., trade name: DIDP, manufactured by Shin Nippon Rika Co., Ltd., trade name: Sansosizer E-PS), sagging inhibitor (manufactured by Enomoto Kasei Co., Ltd., trade name) : Disparon # 305), UV absorber (manufactured by BASF Japan Ltd., trade name: Tinuvin 326), light stabilizer (manufactured by Sankyo Lifetech Co., Ltd., trade name: SANOL LS770), antioxidant (BASF Japan ( Co., Ltd., trade name: Irganox 1010), surface modifier (manufactured by Toagosei Co., Ltd., trade name: Aronix M309), epoxy compound (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Epolite 1600) It weighed accordance recipe of Table 3 was the main agent are dispersed through 3 passes on a three-roll paint mill after thoroughly stirring and mixing. Also, a condensation catalyst (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-28, Wako Pure Chemical Industries, Ltd., trade name: laurylamine), plasticizer (manufactured by Kyowa Hakko Co., Ltd., trade name: DIDP) Heavy calcium carbonate (product name: Whiten SB, manufactured by Shiraishi Calcium Co., Ltd.) and kaolin (product name: Kaolin ASP-170, manufactured by Hayashi Kasei Co., Ltd.) are weighed according to the formulation table in Table 3 and thoroughly stirred. What was mixed with a homogenizer (10000 rpm × 5 minutes) after mixing was used as a curing agent. Furthermore, plasticizer (Kyowa Hakko Co., Ltd., trade name: DIDP) and titanium oxide (Ishihara Sangyo Co., Ltd., trade name: Typek R-820) were weighed according to the recipes in Tables 3 and 4 and fully After stirring and mixing, the toner was dispersed by passing three paint rolls three times.

(Adhesive evaluation)
A mixture obtained by thoroughly stirring and mixing the above main agent, curing agent, and toner is applied to a substrate whose surface has been wiped off with ethanol, and then pressed well with a spatula so that the sealant composition adheres to the substrate, and then cured at room temperature for 7 days. After curing, a cut of about 1 cm is made between the cured product and the base material, and the cured product is grasped by hand so that an angle of 180 ° is formed. Based on the resistance when peeling, it is evaluated in three stages. In the case where CF, TCF, and AF are mixed, the ratio of each destruction state when the whole is 100% is indicated by a number. For example, in a mixed state where CF is 70% and AF is 30%, C70A30 is set.
CF: cohesive failure TCF: thin layer failure AF: interface failure

  Examples 1 to 8 in Table 5 exhibit better adhesion to a high-temperature baking fluorinated aluminum substrate as compared with Comparative Examples 1 to 4 in Table 6.

(Example 9, Comparative Examples 5 and 6)
Polymers obtained in Production Example 1 and Production Example 3, surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Shiraka Hana CCR), heavy calcium carbonate (manufactured by Shiroishi Calcium Co., Ltd., trade name: White) SB), diisodecyl phthalate plasticizer (manufactured by Jay Plus Co., Ltd., trade name: DIDP), dimethyl adipate plasticizer (manufactured by Daihachi Chemical Co., Ltd., trade name: DMA), titanium oxide (Ishihara Sangyo ( Co., Ltd., trade name: Taipei R-820), thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon 6500), UV absorber (BASF Japan Ltd., trade name: Tinuvin 326), Weigh the light stabilizer (Sankyo Lifetech Co., Ltd., trade name: Sanol LS770) and the antioxidant (BASF Japan Co., Ltd., trade name: Irganox 245) with a spatula. After Ku mixing, over a period of 3 passes on a three-roll paint, it was well dispersed. Thereafter, dehydration under reduced pressure is performed at 120 ° C. for 2 hours, and after cooling to 50 ° C. or lower, vinyltrimethoxysilane (product name: A-171) manufactured by Momentive Co., Ltd. -2- (Aminoethyl) -3-aminopropyltrimethoxysilane (manufactured by Momentive Co., Ltd., trade name: A-1122) was added and mixed. Thereafter, dibutyltin acetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-220H) is added as a curing catalyst, and after kneading in a substantially moisture-free state, the composition is put into a moisture-proof container. Was sealed in a cartridge to obtain a one-component curable sealing composition.

  The adhesion with the substrate was evaluated according to the method described above (Evaluation of Adhesiveness). In addition to the evaluation of those cured at 23 ° C. for 7 days, the same evaluation was performed on the test specimens that were cured at 23 ° C. for 7 days and then immersed in warm water at 50 ° C. for 7 days. Table 7 shows the blending composition and adhesion results.

  Comparative Example 5 in Table 7 was inferior in adhesion to acrylic, but the adhesion was improved as in Example 9 by using polymers having different SP values. The amount of the polymer obtained in Production Example 3 is only about 1% by weight of the entire curable composition, and it is based on the knowledge so far that the adhesion to acrylic is greatly improved with such a small amount. I could n’t think of it. In Comparative Example 6, only the polymer obtained in Production Example 3 was used, but the curable composition pulled the yarn and the workability was very poor.

Claims (32)

It has at least one crosslinkable silyl group represented by the general formula (1) and is obtained by polymerizing a (meth) acrylic acid ester represented by the following general formula (2), and measured by gel permeation chromatography. the ratio of the weight average molecular weight to number average molecular weight of Ru polymer der less than 1.8 (meth) acrylate ester polymer (I), and,
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ¹ or When two or more R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
_{CH 2 = C (R) COO} -R 3 (2)
(In the formula, R is a hydrogen atom or a methyl group, and R ³ is an organic group having 1 to 20 carbon atoms.)
20% by weight of (meth) acrylic acid ester having at least one crosslinkable silyl group represented by the general formula (1) and represented by the following general formula (3) and / or the following general formula (4) An organic polymer (II) obtained by polymerizing the above-described monomers and having a solubility parameter (SP value) of 0.2 or more greater than that of the (meth) acrylic acid ester polymer (I),
_{CH 2 = C (R) COO} -R 4 (3)
(In the formula, R is a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 3 carbon atoms.)
_{CH 2 = C (R) COO-} (R 5 -O-) n R 6 (4)
Wherein R is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms or an aralkylene group having 7 to 20 carbon atoms, and R ⁶ is hydrogen. (But only when n is 2 or more), 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, n is an integer of 1 or more, and n ) ^{May be} the same group or different from each other.
A curable composition containing (meth) acrylic acid ester polymer (I) and organic polymer (II) in a weight ratio (I) / (II) of 99/1 to 70/30. The curable composition according to claim 1, wherein the (meth) acrylic acid ester polymer (I) is polybutyl acrylate obtained by polymerizing butyl acrylate. (Meth) acrylic acid ester polymer (I) is (b1) an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms, (b2) an alkyl acrylate having an alkyl group having 4 to 7 carbon atoms, and (B3) The curable composition according to claim 1, wherein the curable composition is obtained by copolymerizing an alkyl acrylate having an alkyl group having 8 to 20 carbon atoms. (B1) The total amount of alkyl acrylate having an alkyl group having 1 to 3 carbon atoms is 1 by weight with respect to the total amount of all (meth) acrylate monomers constituting the (meth) acrylate polymer. % To 30% and the total amount of (b2) alkyl acrylate having an alkyl group of 4 to 7 carbon atoms is the total of (meth) acrylate monomers constituting the (meth) acrylate polymer. (B3) The total amount of alkyl acrylate having an alkyl group of 8 to 20 carbon atoms in the weight ratio with respect to the total amount is 45% or more and 95% or less. The curable composition according to claim 3, wherein the weight ratio is 4% or more and 35% or less with respect to the total amount of the (meth) acrylate monomer. (B1) The total amount of alkyl acrylate having an alkyl group having 1 to 3 carbon atoms is 1 by weight with respect to the total amount of all (meth) acrylate monomers constituting the (meth) acrylate polymer. The curable composition according to claim 4, wherein the curable composition is not less than 20% and not more than 20%. (B2) The total amount of alkyl acrylate having an alkyl group of 4 to 7 carbon atoms is 50 by weight with respect to the total amount of all (meth) acrylate monomers constituting the (meth) acrylate polymer. The curable composition according to claim 4 or 5 , wherein the content is from 95% to 95%. (B2) The total amount of alkyl acrylate having an alkyl group of 4 to 7 carbon atoms is 60 by weight with respect to the total amount of all (meth) acrylate monomers constituting the (meth) acrylate polymer. % Or more and 93% or less, The curable composition of Claim 4 or 5 characterized by the above-mentioned. (B3) The total amount of alkyl acrylate having an alkyl group of 8 to 20 carbon atoms is 6 by weight with respect to the total amount of all (meth) acrylic acid ester monomers constituting the (meth) acrylic acid ester polymer. The curable composition according to any one of claims 4 to 7, wherein the curable composition is not less than 25% and not more than 25%. (B1) The curable composition according to any one of claims 3 to 8, wherein the alkyl acrylate having an alkyl group having 1 to 3 carbon atoms is methyl acrylate and / or ethyl acrylate. (B2) The curable composition according to any one of claims 3 to 9, wherein the alkyl acrylate having an alkyl group having 4 to 7 carbon atoms is butyl acrylate. (B3) The curable composition according to any one of claims 3 to 10, wherein the alkyl acrylate having an alkyl group having 8 to 20 carbon atoms is dodecyl acrylate and / or octadecyl acrylate. The curable composition according to any one of claims 1 to 11, wherein the (meth) acrylic acid ester polymer (I) has a number average molecular weight of 5,000 to 80,000 as measured by gel permeation chromatography. object. The curable composition according to any one of claims 1 to 11, wherein the (meth) acrylic acid ester polymer (I) has a number average molecular weight of 8,000 to 50,000 as measured by gel permeation chromatography. object. (Meth) acrylate ester polymer (I) The curable composition according to any one of claims 1 to 1 3, characterized in that one produced by atom transfer radical polymerization. The organic polymer (II) is a copolymer obtained by copolymerizing a (meth) acrylic acid ester represented by the general formula (3) and / or the general formula (4) and another monomer. the curable composition according to any one of claims 1 to 1 4, characterized. The curable composition according to claim 15 , wherein the other monomer is a vinyl monomer. The organic polymer (meth) acrylic acid ester represented by the general formula (3) in (II), methyl acrylate, ethyl acrylate, any of claims 1 to 1 6, characterized in that the methyl methacrylate The curable composition as described in any one. The (meth) acrylic acid ester represented by the general formula (4) of the organic polymer (II) is 2-methoxyethyl acrylate, according to any one of claims 1 to 17. Curable composition. The curable composition according to any one of claims 1 to 18 , which is a polymer having a number average molecular weight of 500 to 20000 as measured by gel permeation chromatography of the organic polymer (II). The curable composition according to any one of claims 1 to 19 , wherein the organic polymer (II) is produced by free radical polymerization. The curable composition according to any one of claims 1 to 19 , wherein the organic polymer (II) is produced by atom transfer radical polymerization. The curable composition according to any one of claims 1 to 21, wherein the crosslinkable silyl group of the organic polymer (II) is at a terminal. Furthermore represented by the general formula (1), the curable composition according to any one of claims 1-2 2 containing polyether polymer (III) having at least one crosslinkable silyl group. The number-average molecular weight measured by gel permeation chromatography of the polyether polymer (III) is 5,000 or more, the curable composition according to claim 2 3. Polyether polymer (III) in the main chain thereof, the curable composition according to any one of claims 2 3 21 to 24 is essentially polypropylene oxide. Curing characterized in that a molded product obtained by curing the curable composition according to any one of claims 1 to 25 has good adhesion to a substrate coated with a thermoplastic fluororesin. Sex composition. Molded article obtained by curing the curable composition according to any one of claims 1 to 2 6. Sealing material formed using the curable composition according to any one of claims 1 to 2 6. Adhesive comprising the curable composition according to any one of claims 1 to 2 6. Liquid gasket using the curable composition according to any one of claims 1 to 2 6. The curable composition double glazing sealants using according to any one of claims 1 to 2 6. Have a crosslinkable silyl group include the ratio of the weight was measured by gel permeation chromatography average molecular weight to number average molecular weight of Ru polymer der less than 1.8 (meth) acrylate ester-based polymer (I) A method for improving adhesiveness to a substrate by using together an organic polymer (II) having a solubility parameter of 0.2 or more larger than that of (I) in a curable composition.