JP2008274119A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition comprising a vinyl polymer having a crosslinkable silyl group at the terminal which can quickly cure when needed while securing sufficient working time and excels in heat resistance, brake oil resistance, and anti-freeze resistance of a cured product. <P>SOLUTION: The curable composition comprises two components of (I) a vinyl polymer having an average of at least one crosslinkable silyl group at the terminal and (II) a photoacid generator or a photobase generator. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable composition. More specifically, it contains a vinyl polymer (I) having an average of at least one crosslinkable silyl group and a terminal, and a photoacid generator or photobase generator (II). The present invention relates to a curable composition characterized by having expansion resistance when immersed in a non-mineral brake fluid for automobiles defined in K 2233 and an antifreeze liquid (LLC) defined in JIS K 2234.

  Conventionally, many fixed gaskets have been used as sealing materials for automobiles. However, in recent years, liquid gaskets that can be cured by heating and light have been used for the purpose of energy saving and process saving during production. In particular, silicone and radical curable oligomers are used as liquid gasket materials for the purpose of sealing liquid media such as engine oil, brake oil, transmission oil, and antifreeze. Silicone is particularly excellent as a material for liquid gaskets from the viewpoint of heat resistance, but it is mainly used for room temperature curing and heat curing, and it is currently not practically used for photocuring because of cost. It is. Reactive resins (oligomers) for photocuring include urethane acrylates, epoxy acrylates, polyester acrylates, etc., but they do not always satisfy the required performance for the above applications in terms of heat resistance and flexibility. Currently. In particular, there is a strict requirement for sealing performance against brake fluid and antifreeze liquid (hereinafter referred to as LLC), and there is no liquid gasket material that satisfies sealing resistance and heat resistance among photocuring materials. As a cause of insufficient sealing resistance of the above-mentioned photo-curing reactive resin, hydrolysis of an ester bond connecting a radical curable functional group and a polymer (oligomer) main chain is presumed. A curable composition comprising a vinyl polymer having a crosslinkable silyl group at the end as a reactive polymer having no ester bond at the portion connecting the functional group end and the main chain is generally contained at room temperature or in the air. Those that cure with moisture are known (Patent Documents 1 to 11). However, the curing rate of curable compositions using these is generally slow, and when the curing rate is increased due to catalytic activity or the like, the pot life is shortened and the coating operation may be difficult.

  An active energy ray-curable composition of a polymer having a radical polymerizable group such as a (meth) acryloyl group at the terminal as a similar vinyl polymer has recently been reported. (Patent Document 12 to Patent Document 17). However, even in a curable composition using these, in order to introduce a functional group such as a (meth) acryloyl group at the polymer end, it is often necessary to pass through a relatively weak bond such as an ester bond. There is a possibility that such a bond may be cut by LLC, and there has been concern about its use as a sealing material. In addition, there is a problem that an uncured portion is generated in an unexposed portion at the time of curing or the surface becomes uncured due to inhibition of curing by oxygen.

  On the other hand, it has been known for a long time that a crosslinkable silyl group is cross-linked with an acid. Using a similar reaction, a photoacid generator is added to a compound having a crosslinkable silyl group to cure the active energy ray. This is also known (patent documents 18 to 21 and non-patent document 1).

  In many cases, the compound having a crosslinkable silyl group that is cured with active energy rays by adding a photoacid generator is a low molecular weight compound, but an example of a polymer having a crosslinkable silyl group has recently been reported (patents). Reference 22). As this polymer, a polyacrylate vinyl polymer is also shown, but there is no polymer having a crosslinkable silyl group at the terminal, and the vinyl polymer is basically produced by free radical polymerization. There is no precise structural control. If the structure is not precisely controlled, the viscosity becomes high and it is difficult to develop good rubber elasticity.

  There is a report of a photoacid generator-added active energy ray curing for a polyether having a crosslinkable silyl group at the terminal (see Patent Document 23). However, polyethers generally have weak defects in acids, alkalis and salts. Furthermore, the heat resistance, weather resistance, and chemical resistance of the cured product are not high.

Furthermore, although there is a report of photocuring an organic polymer having a hydrolyzed silyl group at the end using a photoacid / base generator (see Patent Document 24), paints, inks, architectural sealing materials, surface protective materials, There is no specific description that it is suitable for adhesives, coating materials and surface treatment agents and can be applied to seals and liquid gaskets for automotive liquid media.
JP 09-272714 A JP-A-11-005815 Japanese Patent Laid-Open No. 11-043512 Japanese Patent Laid-Open No. 11-080571 JP-A-11-116617 JP-A-11-130931 Japanese Patent Laid-Open No. 12-086999 JP-A-12-191912 JP 2000-038404 A JP 2000-044626 A JP 2000-072804 A JP 2000-072816 A JP-A-12-136211 JP-A-12-095826 JP 2001-055551 A JP 2000-154205 A JP 2000-186112 A JP 2000-1648 A JP 2000-169755 A JP 2000-171604 A JP 2000-298352 A JP 2001-515533 A WO2002 / 083764 Japanese Patent No. 3707975 Radiation Curing in Polymer Science and Technology, vol2, Elsevier Applied Science, London, 1993

  As described above, there is a demand for industrial practical application of a composition that can be applied to a site where a liquid gasket or a liquid sealing material has been difficult to apply, and a cured product using the composition.

  Therefore, the object of the present invention is to allow for quick curing when necessary while ensuring a sufficient working time, and the brake fluid resistance, LLC resistance, heat resistance, oil resistance, weather resistance, mechanical properties of the cured product, An object of the present invention is to provide a cured composition that is excellent in adhesiveness and can be used particularly for a liquid gasket or a liquid sealing material.

  As a result of intensive studies, the inventor obtained the following curable composition containing a vinyl-based polymer having a crosslinkable silyl group at its terminal and an acid or base generator by light irradiation, and a cured product thereof. The inventors have found that the object can be achieved and have completed the present invention.

  That is, the present invention relates to a curable composition containing, on average, a vinyl polymer (I) having at least one crosslinkable silyl group at its terminal, and a compound (II) that generates an acid or a base upon irradiation with light. The cured product after curing has expansion resistance in the immersion test of JIS K 6258 using the non-mineral brake fluid for automobiles defined in JIS K 2233 and the antifreeze fluid defined in JIS K 2234. The present invention relates to a curable composition.

  In the curable composition, the cured product may have expansion resistance with a mass and volume change rate of 50% or less before and after liquid immersion in the immersion test of JIS K 6258.

The crosslinkable silyl group may be represented by the general formula (1):
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO. (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. A plurality of R ′ may be the same or different.) ); When two or more of R ¹ or 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 of Y are present, They may be the same or different; a represents 0, 1, 2 or 3; b represents 0, 1, or 2; m represents an integer from 0 to 19, provided that a + mb Satisfy that ≧ 1.)

  The molecular weight distribution of the vinyl polymer (I) may be less than 1.8.

  The main chain of the vinyl polymer (I) may be a (meth) acrylic polymer.

  The (meth) acrylic polymer may be an acrylic polymer, particularly an acrylate polymer.

  The main chain of the vinyl polymer (I) may be produced by a living radical polymerization method.

  The main chain of the vinyl polymer (I) may be produced by an atom transfer radical polymerization method.

  The number average molecular weight of the vinyl polymer (I) may be 3000 or more.

  The main chain of the vinyl polymer (I) may be a polyisobutylene polymer.

  The main chain structure between the crosslinkable silyl group at one end of the vinyl polymer (I) and the crosslinkable silyl group at a position different from the one end is only a carbon-carbon bond, or , Carbon-carbon bonds and carbon-silicon bonds alone.

  The compound (II) that generates an acid or a base upon irradiation with light may be a compound that generates an acid selected from the group consisting of sulfonate esters, onium salts, and carboxylic acid esters.

  The compound (II) that generates an acid or a base upon irradiation with light may be a compound that generates a base selected from the group consisting of carbamates, amides, oxime esters, α-cobalt complexes, and imidazoles.

  The curable composition may further contain an epoxy compound and / or an oxetane compound (III).

  The epoxy compound and / or oxetane compound (III) may be a compound having no aromatic ring.

  The epoxy compound and / or oxetane compound (III) may be a compound having a crosslinkable silyl group in the molecule.

  The curable composition may further contain a compound having a carbon-carbon double bond having radical polymerizability.

  The curable composition may further contain a vinyl polymer (IV) having an average of at least one crosslinkable acryloyl group at the terminal.

The crosslinkable acryloyl group may be represented by the general formula (2).
—OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)

  The vinyl polymer (IV) may have a molecular weight distribution of less than 1.8.

  The main chain of the vinyl polymer (IV) may be a (meth) acrylic polymer.

  The main chain of the vinyl polymer (IV) may be an acrylic polymer, particularly an acrylate polymer.

  The main chain of the vinyl polymer (IV) may be produced by a living radical polymerization method.

  The main chain of the vinyl polymer (IV) may be produced by an atom transfer radical polymerization method.

  The number average molecular weight of the vinyl polymer (IV) may be 3000 or more.

  The curable composition of the present invention may further contain a trialkoxysilane compound or a tetraalkoxysilane compound having a molecular weight of 1000 or less.

  The curable composition of the present invention may further contain a tin-based compound.

  The present invention also relates to a composition for in-situ molded gasket using the curable composition described above.

  Furthermore, this invention relates to the composition for sealing materials which uses the curable composition in any one of said.

  The present invention further relates to a pressure-sensitive adhesive or adhesive composition using any of the curable compositions described above.

  The present invention relates to a composition for a potting agent or a composition for a coating agent using any one of the curable compositions described above.

  This invention relates to the hardened | cured material obtained by irradiating an active energy ray to the composition in any one of said.

  In the immersion test of JIS K 6258, the cured product may have a mass and a volume before and after immersion, and a change rate of strength and elongation at break of tensile properties of JIS K 6251, all at 50% or less.

  The curable composition of the present invention can be quickly cured when necessary while securing a sufficient working time, and is particularly suitable for a liquid gasket or a liquid sealing material. A cured product obtained by curing the curable composition of the present invention is excellent in heat resistance, oil resistance, weather resistance, mechanical properties, adhesiveness, and the like.

The curable composition of this invention is explained in full detail below.
<< About the vinyl polymer (I) >>
Examples of the vinyl polymer (I) having a crosslinkable silyl group at the terminal of the present invention include, for example, JP-A-11-080250, JP-A-11-005815, JP-A-11-116617, JP-A-11-080571, JP-A-11-080571. Polymers disclosed in JP-A-11-130931, JP-A-11-100433, JP-A-11-116763, JP-A-9-272714, JP-A-9-272715 and the like can be used.

The vinyl polymer (I) having a crosslinkable silyl group at the terminal is a vinyl having a reactive terminal as disclosed in JP-A-11-080249, JP-A-11-116606, JP-A-11-080570, and the like. It can be obtained by introducing a crosslinkable silyl group into a polymer.
<Main chain>

It does not specifically limit as a vinyl-type monomer which comprises the principal chain of the vinyl-type polymer of this invention, Various things can be used. To illustrate,
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) Isobutyl acrylate, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-n-heptyl , (Meth) acrylate-n-octyl, (meth) acrylate-2-ethylhexyl, (meth) acrylate nonyl, (meth) acrylate isononyl, (meth) acrylate decyl, (meth) acrylate dodecyl, ( (Meth) acrylic acid phenyl, (meth) acrylic acid tolyl, (meth) acrylic acid benzyl, (meth) acrylic acid-2-methyl Xylethyl, (meth) acrylate-3-methoxybutyl, (meth) acrylate-2-hydroxyethyl, (meth) acrylate-2-hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate, ( (Meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoro Methyl ethyl, perfluoroethyl methyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, perfluoroethyl perfluorobutyl methyl (meth) acrylate, 2-perfluoroethyl-2 (meth) acrylate -Perfluorobutylethyl, (meth) aqua Perfluoroethyl laurate, perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate, 2,2-diperfluoromethyl ethyl (meth) acrylate, perfluoromethyl per (meth) acrylate Fluoroethylmethyl, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, (meth) acrylic (Meth) such as 2-perfluorodecylmethyl acid, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylmethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Acrylic monomers; styrene, vinyl toluene, α-methyl Aromatic vinyl monomers such as styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon such as vinyltrimethoxysilane and vinyltriethoxysilane Containing vinyl monomers; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexyl Maleimide monomers such as maleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; acrylonitrile, meta Acrylonitrile monomers such as acrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; ethylene, propylene, isobutylene Alkenes such as conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used singly or a plurality thereof may be copolymerized.

  It is preferable that the main chain of the vinyl polymer is produced mainly by polymerizing at least one monomer selected from a (meth) acrylic monomer and an isobutylene monomer. Here, “mainly” means that 30 mol% or more, preferably 50 mol% or more of the monomer units constituting the vinyl polymer are the above monomers.

  Among these, a (meth) acrylic acid monomer is preferable from the physical properties of the product. In this specification, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. More preferred are acrylic ester monomers and methacrylic ester monomers, and particularly preferred are acrylic ester monomers. For general architectural use and the like, a butyl acrylate monomer is more preferable from the viewpoint that physical properties such as low viscosity of the blend, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required. On the other hand, in applications that require oil resistance, such as automobile applications, copolymers based on ethyl acrylate are more preferred. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is converted into butyl acrylate. It is also possible to replace it. However, as the ratio of butyl acrylate is increased, the good oil resistance is impaired, so that the ratio is preferably 80 mol% or less depending on the application for which oil resistance is required, and 60 mol% or less. More preferably, it is more preferably 40 mol% or less, and most preferably 30 mol% or less. It is also preferable to use 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, or the like in which oxygen is introduced into the side chain alkyl group in order to improve low-temperature characteristics and the like without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 60 mol% or less, and 40 mol% or less. Is more preferable. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not limited, examples of excellent physical property balance such as oil resistance, heat resistance, and low-temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (molar ratio of 40-50 / 20- 30 / 20-30). Moreover, when using the composition of this invention for an adhesive use, the polymer which has mainly 2-ethylhexyl acrylate / butyl acrylate is preferable.

In addition, when adding an epoxy resin / oxetane resin to the vinyl polymer of the present invention, in order to make the cured product transparent when the curable composition is cured, the vinyl polymer is an epoxy. Those that are compatible with the resin / oxetane resin are preferred, and polymers or copolymers having a higher polarity than the butyl acrylate homopolymer are preferred, and the main chain of the vinyl polymer is represented by the general formula (a). The polymer or copolymer having a repeating unit structure is more preferable.
^{_{- [CH 2 -CR d (COOR}} ")] - ( a)
(Wherein R ^d is hydrogen or a methyl group, R ″ is the same or different and is an alkoxyalkyl group or an alkyl group having 1 to 3 carbon atoms.)

  The polymer or copolymer having a higher polarity than the butyl acrylate homopolymer is not particularly limited, and examples thereof include a copolymer of butyl acrylate and a monomer having a higher polarity than butyl acrylate. Here, examples of the monomer having higher polarity than butyl acrylate include ethyl acrylate and 2-methoxyethyl acrylate. For example, a copolymer of ethyl acrylate / butyl acrylate / acrylic acid 2-methoxyethyl (molar ratio 40-50 / 20-30 / 20-30) is easily compatible with various epoxy resins, and is a transparent cured product. Since it is easy to obtain, it is suitable.

  Copolymerizes monomers with long-chain alkyl groups such as stearyl groups and lauryl groups to improve compatibility with other polymers such as modified silicone resins (oxyalkylene polymers having crosslinkable silyl groups) You may let them. Although there is no particular limitation, for example, 5-30 mol% of stearyl acrylate or lauryl acrylate is copolymerized so that the compatibility with the modified silicone resin becomes very good. Since the compatibility varies depending on the molecular weight of each polymer, it is preferable to select the proportion of the monomer to be copolymerized accordingly. In this case, block copolymerization may be performed. By block copolymerization, the effect may be manifested in a small amount.

  A curable composition containing a vinyl polymer having a functional silyl group may be slow in curability upon storage, that is, poor in storage stability. In such a case, for example, the phenomenon can be suppressed by copolymerizing methyl acrylate. Also, it is effective to copolymerize methyl acrylate when it is desired to improve the strength of the cured product. The ratio of the monomer to be copolymerized may be selected according to the molecular weight, and further block copolymerization may be performed.

  In the present invention, these preferable monomers can be copolymerized with other monomers, and further block copolymerized. In that case, it is preferable that these preferable monomers are contained in a weight ratio of 40% or more.

  The molecular weight distribution of the vinyl polymer of the present invention, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography is not particularly limited. A molecular weight distribution of less than 1.8, particularly 1.3 or less is preferable from the viewpoint of workability. In the GPC measurement in the present invention, chloroform is usually 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 in the present invention is not particularly limited. In addition, when measured by gel permeation chromatography, 500 to 1,000,000, particularly 3,000 to 50,000, and more preferably 10,000 or more are preferable from the viewpoint of workability and physical properties. Of course, the smaller the molecular weight, the easier it is to be compatible with other resins (various polymers), and the resulting cured product tends to have a high modulus and low elongation. Conversely, if the molecular weight is large, the opposite is true. Show the trend.

<Synthesis of main chain>
The method for synthesizing the vinyl polymer in the present invention is not limited and may be synthesized by free radical polymerization. However, controlled radical polymerization is preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is particularly preferable. . These will be described below. The isobutylene polymer is preferably prepared by living cationic polymerization.

Controlled radical polymerization The radical polymerization method is a "general radical polymerization method" in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound or peroxide as a polymerization initiator. Can be classified into “controlled radical polymerization methods” in which a specific functional group can be introduced at a controlled position such as a terminal.

  A general radical polymerization method is simple, but a monomer having a specific functional group is introduced into the polymer only probabilistically. It is necessary to use a considerable amount of monomer. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

  The controlled radical polymerization method is a “chain transfer agent method” in which a vinyl polymer having a functional group at the terminal is obtained by polymerization using a chain transfer agent having a specific functional group, and the polymerization growth terminal is terminated. It can be classified as a “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing without causing the above.

  The “chain transfer agent method” can obtain a polymer having a high functionalization rate, but requires a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator. Further, like the above-mentioned “general radical polymerization method”, since it is free radical polymerization, only a polymer having a wide molecular weight distribution and high viscosity may be obtained.

  Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

  Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing a vinyl polymer having the specific functional group is more preferable.

  In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows. In general and in this specification, the terminal is inactivated. And pseudo-living polymerization in which the activated product grows in an equilibrium state.

  As the “living radical polymerization method”, for example, a method using a cobalt porphyrin complex as shown in Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules, using a radical capping agent such as a nitroxide compound as shown in Macromolecules, 1994, Vol. 27, p. 7228, “Atom transfer using organic halides as initiators and transition metal complexes as catalysts” Radical polymerization "(Atom Transfer Radical Polymerization: ATRP).

  Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above “living radical polymerization method”. In addition to the features of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts, so the production of vinyl polymers having specific functional groups More preferable as a method. As this atom transfer radical polymerization method, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules 1995 28, 7901, Science 1996, 272, 866, WO 96/30421, WO 97/18247, WO 98/01480, WO 98/40415, or Sawamoto et al., Macromore. Examples include the methods described in Macromolecules 1995, 28, 1721, JP-A-9-208616, and JP-A-8-41117.

  In the present invention, a living radical polymerization, particularly an atom transfer radical polymerization method is preferred as the polymerization method.

  Hereinafter, each polymerization method will be described in detail. First, the polymerization using a chain transfer agent (telomer), which is one of the controlled radical polymerizations that can be used for producing a vinyl polymer, is not particularly limited, but has a terminal structure suitable for the present invention. The following two methods are exemplified as the method for obtaining the vinyl polymer.

  That is, a method for obtaining a halogen-terminated polymer using a halogenated hydrocarbon as a chain transfer agent as disclosed in JP-A-4-132706, JP-A-61-271306, and JP-A-2594402. JP-A-54-47782 discloses a method of obtaining a hydroxyl-terminated polymer using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent.

  Next, living radical polymerization will be described.

  First, in a method using a radical capping agent such as a nitroxide compound, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Examples of such compounds include, but are not limited to, compounds described in paragraph [0055] of WO2007 / 029733. Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

  The radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator and the polymerization of the addition polymerizable monomer proceeds. The combination ratio of both is not particularly limited, but 0.1 to 10 mol of the radical generator is suitable for 1 mol of the radical capping agent.

  Although various compounds can be used as the radical generator, a peroxide capable of generating a radical under polymerization temperature conditions is preferred. Examples of the peroxide include, but are not limited to, compounds described in paragraph [0056] of WO2007 / 029733. Benzoyl peroxide is particularly preferable. Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.

アルコキシアミン化合物を開始剤として用いる場合、それが上図で示されているような水酸基等の官能基を有するものを用いると、末端に官能基を有する重合体が得られる。これを本発明の方法に利用すると、末端に官能基を有する重合体が得られる。 Macromolecules 1995, 28, P.M. As reported in 2993, instead of using a radical capping agent and a radical generator in combination, the following alkoxyamine compound may be used as an initiator.

When an alkoxyamine compound is used as an initiator, if it has a functional group such as a hydroxyl group as shown in the above figure, a polymer having a functional group at the terminal can be obtained. When this is used in the method of the present invention, a polymer having a functional group at the terminal can be obtained.

  The polymerization conditions such as the monomer, solvent, polymerization temperature and the like used in the polymerization using a radical capping agent such as the above nitroxide compound are not limited, but may be the same as those used for the atom transfer radical polymerization described below.

Atom Transfer Radical Polymerization Next, a more preferred atom transfer radical polymerization method as the living radical polymerization of the present invention will be described.

  In this 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 halogenated compound. A sulfonyl compound or the like is used as an initiator. Specific examples include the compounds described in paragraph [0062] of WO2007 / 029733.

  As an initiator of atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a functional group at one end of the main chain and a growth terminal structure of atom transfer radical polymerization at the other main chain end is produced. Examples of such functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like.

It does not limit as an organic halide which has an alkenyl group, For example, what has a structure shown in General formula (3) is illustrated.
^{R 4 R 5 C (X)} -R 6 -R 7 -C (R 3) = CH 2 (3)
(Wherein R ³ is hydrogen or a methyl group, R ⁴ and R ⁵ are hydrogen, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, or interconnected at the other end. things, ^{R 6} is, -C (O) O- (ester group), - C (O) - ( keto group), or o-, m-, p-phenylene group, ^{R 7} is a direct bond or carbon atoms 1 to 20 divalent organic groups which may contain one or more ether bonds, X is chlorine, bromine or iodine)

Specific examples of the substituents R ⁴ and R ⁵ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. R ⁴ and R ⁵ may be linked at the other end to form a cyclic skeleton.

  The compound represented by the general formula (3) is not particularly limited, and examples thereof include known compounds (for example, compounds described in paragraphs [0065] to [0069] of WO2007 / 029733).

Examples of the organic halide having an alkenyl group further include a compound represented by the general formula (4).
_{^{H 2 C = C (R 3}} ) -R 7 -C (R 4) (X) -R 8 -R 5 (4)
(Wherein R ³ , R ⁴ , R ⁵ , R ⁷ and X are the same as above, R ⁸ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group) Or an o-, m-, p-phenylene group)
R ⁷ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), and in the case of a direct bond, carbon to which a halogen is bonded Is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group or a phenylene group as R ⁸ , and a direct bond may be used. When R ⁷ is not a direct bond, R ⁸ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

  The compound of the general formula (4) is not particularly limited, and examples thereof include known compounds (for example, compounds described in paragraph [0070] of WO2007 / 029733).

If the specific example of the sulfonyl halide compound which has an alkenyl group is given,
_{o-, m-, p-CH 2} = CH- (CH 2) n -C 6 H 4 -SO 2 X, o-, m-, p-CH 2 = CH- (CH 2) n -O-C ₆ H ₄ —SO ₂ X (in the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20).

It does not specifically limit as an organic halide which has a crosslinkable silyl group, For example, what has a structure shown to General formula (5) is illustrated.
^{R 4 R 5 C (X)} -R 6 -R 7 -C (H) (R 3) CH 2 - [Si (R 9) 2-b (Y) b O] m -Si (R 10) 3- _a (Y) _a (5)
(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X are the same as above, and R ⁹ and R ¹⁰ are all alkyl groups, aryl groups, aralkyl groups having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). Represents an organosiloxy group, and when two or more R ⁹ or R ¹⁰ are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and Y represents two or more When present, 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 from 0 to 19. (Provided that a + mb ≧ 1)
The compound of the general formula (5) is not particularly limited, and examples thereof include known compounds (for example, compounds described in paragraph [0072] of WO2007 / 029733).

Examples of the organic halide having a crosslinkable silyl group further include those having a structure represented by the general formula (6).
_{^{(R 10) 3-a (}} Y) a Si- [OSi (R 9) 2-b (Y) b] m -CH 2 -C (H) (R 3) -R 7 -C (R 4) ( X) —R ⁸ —R ⁵ (6) (wherein R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , a, b, m, X, Y are the same as above) . Examples thereof include those having the structure described in paragraph [0073] of WO 2007/029733.

  The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include known compounds (for example, compounds described in paragraph [0074] of WO2007 / 029733).

  The organic halide having an epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include known compounds (for example, compounds described in paragraph [0075] of WO2007 / 029733).

（式中、Ｘは塩素、臭素、またはヨウ素、Ｒは水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）
等が挙げられる。 In order to obtain a polymer having two or more growth terminal structures in one molecule, it is preferable to use an organic halide having two or more starting points or a sulfonyl halide compound as an initiator. For example,

(In the formula, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
Etc.

  There is no restriction | limiting in particular as a vinyl-type monomer used in atom transfer radical polymerization, All already illustrated 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 preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as a polyamine is added. A preferred ligand is a nitrogen-containing compound, a more preferred ligand is a chelate-type nitrogen-containing compound, and a more preferred ligand is N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine. It is. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Furthermore, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

  The polymerization can be carried out without solvent or in various solvents. Examples of the solvent include those described in paragraph [0082] of WO2007 / 029733, and may be used alone or in admixture of two or more.

  Moreover, although not limited, superposition | polymerization can be performed in 0 to 200 degreeC, Preferably it is 50 to 150 degreeC.

  The atom transfer radical polymerization of the present invention includes so-called reverse atom transfer radical polymerization. Reverse atom transfer radical polymerization is a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, peroxidation with respect to Cu (II ′) when Cu (I) is used as a catalyst. In this method, a general radical initiator such as a compound is allowed to act, and as a result, an equilibrium state similar to that of atom transfer radical polymerization is produced (see Macromolecules 1999, 32, 2872).

<Functional group>
Number of crosslinkable silyl groups The vinyl polymer (I) of the present invention has at least one crosslinkable silyl group on average at its molecular end. From the viewpoint of the curability of the composition and the physical properties of the cured product, the crosslinkable silyl group is preferably 1.2 or more and 3.5 or less, more preferably 1.4 or more and 2 in average in the molecule. There are less than one.

Position of the crosslinkable silyl group Since the crosslinkable silyl group of the vinyl polymer (I) of the present invention is present at the molecular end, the molecular weight between the crosslink points having a great influence on rubber elasticity can be increased. Good rubber properties can be imparted to a cured product obtained by curing the composition. The crosslinkable silyl group may be present other than at the molecular end, but more preferably, all the crosslinkable functional groups are present at the molecular chain end.

  A method for producing a vinyl polymer having at least one crosslinkable silyl group at the molecular chain end, in particular, a (meth) acrylic polymer is disclosed in Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, This is disclosed in, for example, Kaihei 6-221922. 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 In general, the molecular weight distribution represented by may be as large as 2 or more, and the viscosity may be high. 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.

Crosslinkable silyl group As a crosslinkable silyl group of this invention, General formula (1);
^{_{- [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 ¹¹ or When two or more R ¹² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, 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. }
The group represented by these is mention | raise | lifted.

  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 (7)
-Si (R ² ) _3-a (Y) _a (7)
A crosslinkable silyl group represented by the formula (wherein R ² and Y are the same as described above, and 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 may be used. In particular, when a very fast curing rate is required, such as when used at low temperatures, the curing rate is not sufficient, and if it is desired to give flexibility after curing, it is necessary to reduce the crosslinking density, Therefore, since the crosslinking density is not sufficient, stickiness (surface tack) can appear. In that case, it is preferable that a is 3 (for example, a trimethoxy functional group).

  Further, a group having a of 3 (for example, a trimethoxy functional group) cures faster than a group having 2 (for example, a dimethoxy functional group), but may be inferior in terms of storage stability and mechanical properties (elongation, etc.). In order to achieve a balance between curability and physical properties, a group having a 2 (for example, a dimethoxy functional group) and a group 3 (for example, a trimethoxy functional group) may be used in combination.

  For example, when a is 2 or more and Y is the same, the reactivity of Y increases as a increases. On the other hand, by selecting Y from different groups and adjusting a, it is possible to control the curability and the mechanical properties of the cured product, and Y and a can be selected according to the purpose and 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. By setting it as such a composition, it can be set as the composition which has low viscosity before hardening, high elongation at break after hardening, low bleed property, low surface contamination property, and excellent paint adhesion.

Method for Introducing Crosslinkable Silyl Group Hereinafter, a method for introducing a crosslinkable silyl group into the vinyl polymer of the present invention will be exemplarily described, but the present invention is not limited thereto.

  As an example, the method described in paragraphs [0093] to [0134] of WO2007 / 029733 can be used.

Specifically, (A) a method in which a hydrosilane compound having a crosslinkable silyl group is added to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst; (B) vinyl having at least one hydroxyl group A method of reacting a compound having a group capable of reacting with a hydroxyl group, such as a compound having a crosslinkable silyl group and an isocyanate group in one molecule; (C) when synthesizing a vinyl polymer by radical polymerization A method of reacting a compound having a polymerizable alkenyl group and a crosslinkable silyl group in one molecule; (D) a chain transfer agent having a crosslinkable silyl group when synthesizing a vinyl polymer by radical polymerization; How to use;
(E) A method in which a vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a compound having a crosslinkable silyl group and a stable carbanion in one molecule.

  The vinyl 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 a vinyl polymer is synthesized by radical polymerization, a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule is reacted as a second monomer.
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 vinyl polymer by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. A method of reacting a compound having at least two alkenyl groups having low polymerizability, such as

  (Ac) Various organometallic compounds having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin on a vinyl polymer having at least one highly reactive carbon-halogen bond A method of replacing halogen by reaction.

  (Ad) A method in which halogen is substituted by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having an alkenyl group.

  (Ae) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with, for example, a single metal such as zinc or an organometallic compound. A method of reacting with an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group .

  (Af) A method in which halogen is substituted by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with an oxyanion or carboxylate anion having an alkenyl group.

  The above-described method for synthesizing a vinyl polymer having at least one carbon-halogen bond having high reactivity 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.

Moreover, the vinyl 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. In the hydroxyl group of a vinyl polymer having at least one hydroxyl group,
(Ag) A method in which a base such as sodium methoxide is reacted and reacted 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 a halogen is not directly involved in a method for introducing an alkenyl group such as (Aa) and (Ab), it is preferable to synthesize a vinyl polymer using a living radical polymerization method. The method (Ab) is more preferable from the viewpoint of easier control.

  When an alkenyl group is introduced by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide having at least one highly reactive carbon-halogen bond, or A vinyl heavy polymer having at least one highly reactive carbon-halogen bond at the terminal, obtained by radical polymerization of a vinyl monomer using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization method). It is preferable to use coalescence. In view of easier control, the method (Af) is more preferable.

Although there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group, Typically, the compound shown by General formula (8):
^{_{H- [Si (R 1 2-}} b) (Y b) O] m -Si (R 2 3-a) Y a (8)
(In the formula, R ¹ , R ² , Y, a, b and m are the same as described above. When two or more R ¹ or R ² 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 (9)
H-Si (R ² _{3-a ′} ) Y _{a ′} (9)
(In the formula, R ² and Y are the same as described above. A ′ is an integer of 1 to ^3. )
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 reacted with an alkenyl group, a transition metal catalyst is usually used. Examples of transition metal catalysts 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.

  Examples of the method for producing a vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) include the following methods, but are limited to these methods. It is not something.

  (Ba) A method of reacting, as a second monomer, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule when a vinyl polymer is synthesized by radical polymerization. There is no limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule. However, particularly in the case of living radical polymerization, when the rubber-like properties are expected, the end of the polymerization reaction or a predetermined monomer. After completion of the reaction, it is preferable to react as the second monomer.

(Bb) When a vinyl polymer is synthesized by living radical polymerization, an alkenyl alcohol such as 10-undecenol, 5-hexenol or allyl alcohol is reacted at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. How to make.

(Bc) A method in which a vinyl monomer is radically polymerized using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide described in JP-A-5-262808.

(Bd) A method of radical polymerization of a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as disclosed in, for example, JP-A-6-239912 and JP-A-8-283310.

(Be) A method of radical polymerization of a vinyl monomer by using an excessive amount of alcohol as disclosed in, for example, JP-A-6-116312.

(Bf) Hydrolysis of a vinyl polymer having at least one highly reactive carbon-halogen bond or reaction with a hydroxyl group-containing compound by a method such as disclosed in JP-A-4-132706. To introduce a hydroxyl group into the terminal.

(Bg) A method in which a vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group to substitute a halogen.

(Bh) An enolate anion is prepared by allowing a metal polymer such as zinc or an organometallic compound to act on a vinyl polymer having at least one highly reactive carbon-halogen bond, and then aldehydes. Or a method of reacting ketones.

(Bi) A method in which a halogen-substituted oxyanion or carboxylate anion is reacted with a vinyl polymer having at least one highly reactive carbon-halogen bond.
(Bj) When synthesizing a vinyl polymer by living radical polymerization, as the second monomer after the end of the polymerization reaction or after the completion of the reaction of the predetermined monomer, an alkenyl group and a hydroxyl group having low polymerizability in one molecule The method of making the compound which has this react.

  In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group such as (Ba) to (Be) and (Bj), a vinyl polymer is obtained by using a living radical polymerization method. It is preferable to synthesize. The method (Bb) is more preferable in terms of easier control.

  When introducing a hydroxyl group by converting halogen in a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide or a sulfonyl halide compound is used as an initiator, and a transition metal complex is used as a catalyst. It is preferable to use a vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by radical polymerization of a vinyl monomer (atom transfer radical polymerization method). The method (Bi) is more preferable from the viewpoint of easier control.

  Examples of the compound having a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and γ-isocyanate. Examples thereof include natopropyltriethoxysilane, and a generally known catalyst for urethanization reaction can be used if necessary.

  Examples of the compound having a polymerizable alkenyl group and a crosslinkable silyl group in one molecule used in the method (C) include trimethoxysilylpropyl (meth) acrylate and methyldimethoxysilylpropyl (meth) acrylate. There is no particular limitation on the timing for reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule. However, particularly in the case of living radical polymerization, when the rubber-like properties are expected, the end or place of the polymerization reaction is considered. It is preferable to react as the second monomer after completion of the reaction of the constant monomer.

Examples of the chain transfer agent having a crosslinkable silyl group used in the chain transfer agent method of (D) include mercaptans having a crosslinkable silyl group and crosslinkable silyl as shown in, for example, Japanese Patent Publication Nos. 3-14068 and 4-55444. And hydrosilane having a group.

The method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond, which is used in the method (E), uses an organic halide as described above as an initiator, and a transition metal complex. Examples thereof include, but are not limited to, an atom transfer radical polymerization method using a catalyst.

Examples of the compound having both a crosslinkable silyl group and a stabilized carbanion in one molecule include those represented by the general formula (21).
^{M + C - (R 13)} (R 14) -R 15 -C (H) (R 16) -CH 2 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) _3-a (Y) _a (10)
(Wherein R ¹ , R ² , R ¹³ , R ¹⁴ , Y, a, b, m are the same as above. R ¹⁵ is a direct bond or one divalent organic group having 1 to 10 carbon atoms. R ¹⁶ which may contain the above ether bond represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.)
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.
<Use of multiple vinyl polymers>
The above-mentioned vinyl polymer (I) may be a single polymer or a blend that is a combination of two or more vinyl polymers. When only one kind is used, it is preferable to use a vinyl polymer having a molecular weight of 5,000 to 50,000 and a number of crosslinkable silyl groups of 1.2 to 3.5. When combining two or more kinds of vinyl polymers, the first polymer is a vinyl polymer having a molecular weight of 5,000 to 50,000 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 polymer having a low molecular weight component preferably has a molecular weight of less than 10,000, more preferably less than 5,000, and the preferred number of crosslinkable silyl groups is less than 1.2, and further 1 or less. Further, since the viscosity can be further reduced, the molecular weight distribution is preferably less than 1.8. When a vinyl 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 a polymer having such a low molecular weight and a small number of crosslinkable silyl groups, it is definitely possible to use a vinyl polymer having a crosslinkable silyl group at one end obtained by the following production method. It is preferable because it can be introduced.
A vinyl polymer having a crosslinkable silyl group at one end has approximately one crosslinkable silyl group per molecule at the end of the polymer. 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 vinyl 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 in which a polymer having one highly reactive carbon-halogen bond per molecule per molecule is reacted 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. More specifically, the method described in paragraphs [0131] to [0137] of WO2007 / 029733 can be mentioned.
The vinyl polymer having a crosslinkable silyl group at one end, preferably a polymer having a molecular weight distribution of less than 1.8, is used as a vinyl polymer having more than one crosslinkable silyl group at the molecular end. It is preferable that it is 5-400 weight part with respect to 100 weight part of polymers from the point of a modulus and elongation.
As a second embodiment in which two or more kinds of vinyl polymers are used in combination, a vinyl polymer having a molecular weight distribution of 1.8 or more and a vinyl polymer having a molecular weight distribution of less than 1.8 can be used in combination. . 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. As the main chain of the vinyl polymer having a molecular weight distribution of less than 1.8, used as the first polymer, the vinyl polymer having a molecular weight distribution of 1.8 or more, or the second polymer, Polymers derived from the vinyl monomers mentioned can be used, and both polymers are preferably acrylate polymers. Even when such a combination of two or more vinyl polymers is used, the vinyl copolymer (I) of the present invention as a whole has an average of at least one crosslinkable silyl group at the end.

  A vinyl polymer having a molecular weight distribution of 1.8 or more can be obtained by a usual vinyl 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.

Other methods for introducing a crosslinkable silyl group include, for example, a method in which a compound having both a polymerizable unsaturated bond and a crosslinkable silyl group is copolymerized with a (meth) acrylate monomer unit. It is done. As a compound having both a polymerizable unsaturated bond and a crosslinkable silyl group, the general formula (11):
_{^{CH 2 = C (R 17)}} COOR 18 - [Si (R 1 2-b) (Y b) O] m Si (R 2 3-a) Y a (11)
(In the formula, R ¹⁷ is the same as above. R ¹⁸ is a divalent alkylene group having 1 to 6 carbon atoms. R ¹ , R ² , Y, a, b and m are the same as above.)
Or general formula (12):
_{^{CH 2 = C (R 17)}} - [Si (R 1 2-b) (Y b) O] m Si (R 2 3-a) Y a (12)
(In the formula, R ¹⁷ , R ¹ , R ² , Y, a, b, m are the same as above.)
There is a monomer represented by Examples of such compounds include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl polyalkoxysilane such as γ-methacryloxypropyltriethoxysilane, and γ-acryloxy. Vinyl such as γ-acryloxypropyl polyalkoxysilane such as propyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane Examples thereof include 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. .

  A vinyl polymer having a crosslinkable functional group and having a molecular weight distribution of 1.8 or more preferably has a number average molecular weight of 500 to 100,000 in terms of polystyrene as measured by GPC. Furthermore, the thing of 1,500-30,000 is more preferable from the weather resistance of a hardened | cured material, and workability | operativity being favorable.

<< Polyisobutylene polymer >>
As the vinyl polymer (I) having a crosslinkable silyl group at the terminal of the present invention, a polyisobutylene polymer is also preferable.
<Main chain>
In the polyisobutylene polymer, all of the monomer units may be formed from isobutylene units, or monomer units having copolymerizability with isobutylene are preferably 50% or less (weight) in the isobutylene polymer. %, The same shall apply hereinafter), more preferably 30% or less, particularly preferably 10% or less. Examples of such monomer components include olefins, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes described in WO2007 / 029733.

  In addition, when vinyl silanes or allyl silanes are used as monomers copolymerizable with isobutylene, the silicon content increases and the number of groups that can act as a silane coupling agent increases. improves. In the hydrogenated polybutadiene polymer and other saturated hydrocarbon polymers, as in the case of the isobutylene polymer, other monomer units are included in addition to the main monomer unit. May be.

  In the main chain of the polyisobutylene polymer of the present invention, a monomer unit such that a double bond remains after polymerization, such as a polyene compound such as butadiene and isoprene, within a range in which the object of the present invention is achieved. May be contained in a small amount, preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less. The number average molecular weight of the saturated hydrocarbon polymer, preferably an isobutylene polymer or hydrogenated polybutadiene polymer, is preferably about 500 to 50,000, and particularly liquid or fluid of about 1,000 to 30,000. It is preferable from the viewpoint of easy handling.

<Synthesis of main chain>
The method for synthesizing the main chain of the polyisobutylene polymer of the present invention is not limited, but living cationic polymerization is preferred from the viewpoint of easy control of molecular weight and functional group introduction.
Living cationic polymerization Living cationic polymerization is a polymerization method that suppresses isomerization, chain transfer reaction, and termination reaction of growing carbenium ions, which is a problem of cationic polymerization. This is a polymerization that proceeds. Apparently, like the above-mentioned living radical polymerization, the one in which the terminal is inactivated and the one in which the terminal is activated are grown while being in an equilibrium state. Examples of living cation polymerization are reported by Higashimura et al. (Macromolecules, 17, 265, 1984) in which vinyl ether is polymerized using a combination of hydrogen iodide and iodine, Kennedy et al. JP-A-64-62308), which is obtained by polymerizing an olefin monomer such as isobutylene in combination with a Lewis acid using an organic carboxylic acid, ester or ether as an initiator.

Although there is no limitation in the living cationic polymerization, the cationic polymerizable monomer is polymerized in the presence of a compound represented by the following general formula (13).
(CR ¹⁹ R ²⁰ X) _n R ²¹ (13)
(Wherein X is a halogen atom, a substituent selected from an alkoxy group having 1 to 6 carbon atoms or an acyloxy group, R ¹⁹ and R ²⁰ are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ¹⁹ , R ²⁰ may be the same or different, R ²¹ is a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group, and n represents a natural number of 1 to 6.)

Monomer for Living Cationic Polymerization The monomer used for the living cationic polymerization of the present invention is not particularly limited, but a monomer constituting the main chain of the polymer (I) can be used, and is preferably isobutylene.
Initiator for Living Cationic Polymerization The compound represented by the general formula (12) serves as an initiator, and is considered to generate a carbon cation in the presence of a Lewis acid or the like and serve as a starting point for cationic polymerization. Examples of the compound of the general formula (12) used in the present invention are not particularly limited, and known compounds can be used (for example, compounds described in paragraph [0148] of WO2007 / 029733).

Of these, bis (1-chloro-1-methylethyl) benzene [C ₆ H ₄ (C (CH ₃ ) ₂ Cl) ₂ ] is particularly preferable [bis (1-chloro-1-methylethyl) Benzene is also called bis (α-chloroisopropyl) benzene, bis (2-chloro-2-propyl) benzene or dicumyl chloride]. This is a bifunctional initiator. When polymerization is started from this, a polymer having both ends as growth ends is obtained.

Living Cationic Polymerization Catalyst In the case of living cationic polymerization, a Lewis acid catalyst can also be present. Such Lewis acid may be any one that can be used for cationic polymerization. TiCl ₄ , TiBr ₄ , BCl ₃ , BF ₃ , BF ₃ .OEt ₂ , SnCl ₄ , SbCl ₅ , SbF ₅ , WCl ₆ , TaCl ₅ , VCl ₅ , FeCl ₃ , ZnBr ₂ , AlCl ₃ , AlBr _{3 and} other metal halides; Et ₂ AlCl, EtAlCl _{2 and} other organic metal halides can be suitably used. Of these, TiCl ₄ , BCl ₃ , and SnCl ₄ are preferable in view of the ability as a catalyst and industrial availability. The amount of Lewis acid used is not particularly limited, but can be set in view of the polymerization characteristics or polymerization concentration of the monomer used. Usually, it is 0.1-100 mol equivalent with respect to the compound represented by General formula (12), Preferably it is the range of 1-60 mol equivalent.

Electron Donor Component for Living Cationic Polymerization In the living cationic polymerization, an electron donor component can be further present if necessary. This electron donor component is considered to have an effect of stabilizing the growing carbon cation during cationic polymerization, and a polymer having a controlled structure with a narrow molecular weight distribution is formed by the addition of the electron donor. The electron donor component that can be used is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom.

Polymerization Conditions for Living Cationic Polymerization Living cationic polymerization can be carried out in a solvent as necessary, and any solvent can be used without any particular limitation as long as it does not substantially inhibit cationic polymerization. Specific examples include those described in paragraph [0148] of WO2007 / 029733. Among these, 1-chlorobutane can be preferably used from the balance of solubility of the polymer, easiness of detoxification by decomposition, cost, and the like.

  These solvents are used alone or in combination of two or more in consideration of the balance of the polymerization characteristics of the monomers constituting the polymer and the solubility of the polymer to be produced. The amount of the solvent used is determined so that the concentration of the polymer is 1 to 50 wt%, preferably 5 to 35 wt%, in consideration of the viscosity of the polymer solution obtained and the ease of heat removal.

  In carrying out the actual polymerization, the respective components are mixed at a temperature of, for example, −100 ° C. or more and less than 0 ° C. under cooling. In order to balance the energy cost and the stability of polymerization, a particularly preferred temperature range is −30 ° C. to −80 ° C.

<Crosslinkable silyl group>
A method for introducing a crosslinkable silyl group into a polyisobutylene polymer will be described below.

A method for producing an isobutylene polymer having a crosslinkable silyl group will be described below. In general, among saturated hydrocarbon polymers having a crosslinkable silyl group, a saturated hydrocarbon polymer having a crosslinkable silyl group at the molecular chain terminal is a polymerization method called an inifer method (an initiator called an inifer) It can be produced using a terminal functional type, preferably an all terminal functional saturated hydrocarbon polymer obtained by a cationic polymerization method using a specific compound also serving as a chain transfer agent. As a method for producing a saturated hydrocarbon polymer having a crosslinkable silyl group, for example, a dehydrohalogenation reaction at a terminal of a polymer having a tertiary carbon-chlorine bond obtained by a polymerization reaction or a tertiary carbon-chlorine bond can be used. After obtaining polyisobutylene having an unsaturated group at the terminal by reaction of the terminal of the polymer having with allyltrimethylsilane, etc., the general formula (8);
^{_{H- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (8)
{Wherein R ¹ , R ² , Y, a, b, and m are the same as described above. However, it shall be satisfied that a + mb ≧ 1. }
Among these hydrosilane compounds, in particular, the general formula (9)
_{^{H-Si (R 2) 3}} -a '(Y) a' (9)
(In the formula, R ² , Y and a ′ are the same as above.)
It can obtain by reaction (hydrosilylation reaction) which adds the hydrosilane compound represented by these using a platinum catalyst. Examples of the hydrosilane compound include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane. Alkoxysilanes; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; ketoximatesilanes such as bis (dimethylketoxymate) methylsilane and bis (cyclohexylketoxymate) methylsilane However, it is not limited to these. Of these, halogenated silanes and alkoxysilanes are particularly preferred.

  Such a production method is described in, for example, each specification of JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, and JP-A-2539445. Are listed. An isobutylene polymer having a crosslinkable silyl group in the molecular chain is produced by adding vinylsilanes or allylsilanes having a crosslinkable silyl group to a monomer containing isobutylene and copolymerizing them.

  Furthermore, in the polymerization reaction for producing an isobutylene polymer having a crosslinkable silyl group at the molecular chain terminal, vinylsilanes or allylsilanes having a crosslinkable silyl group were copolymerized in addition to the main component isobutylene monomer. Then, by introducing a crosslinkable silyl group at the terminal, an isobutylene polymer having a crosslinkable silyl group at the terminal and in the molecular chain is produced.

  Examples of vinylsilanes and allylsilanes having a crosslinkable silyl group include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, allyltrichlorosilane, and allylmethyldichlorosilane. Allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and the like.

In the present invention, examples of the saturated hydrocarbon polymer having a crosslinkable silyl group include a hydrogenated polybutadiene polymer having a crosslinkable silyl group. A hydrogenated polybutadiene polymer having a crosslinkable silyl group can be obtained by a hydrosilylation reaction of a hydrogenated polybutadiene polymer having an olefin group. The hydrogenated polybutadiene-based polymer having a terminal olefin group is, for example, first made a hydroxyl group of a terminal hydroxy-hydrogenated polybutadiene-based polymer with an oxymetal group such as -ONa or -OK, and then represented by the general formula (14):
^{_{CH 2 = CH-R 22 -Y}} (14)
Wherein, Y is a chlorine atom, a bromine atom, a halogen atom such as iodine ^{atom, R 22} is ^-R 23 ^{-, -} R 23 -OCO- or ^{-R 23} -CO- ^(R 23 is 1 to 20 carbon atoms A divalent hydrocarbon group, preferably an alkylene group, a cycloalkylene group, an arylene group or an aralkylene group), and represented by —CH ₂ —, —R ²⁴ —C ₆ H ₄ —CH ₂ — (R ²⁴ is preferably a divalent group selected from hydrocarbon groups having 1 to 10 carbon atoms) can be obtained by reacting with an organic halogen compound.

The method for converting the terminal hydroxyl group of the terminal hydroxy-hydrogenated polybutadiene polymer to an oxymetal group includes alkali metals such as Na and K; metal hydrides such as NaH; metal alkoxides such as NaOCH ₃ ; alkaline water such as NaOH and KOH. The method of making it react with an oxide etc. is mention | raise | lifted. In the above method, a terminal olefin hydrogenated polybutadiene polymer having almost the same molecular weight as that of the terminal hydroxy hydrogenated polybutadiene polymer used as a starting material can be obtained. Before reacting the organic halogen compound of formula (14), a polyvalent organic halogen compound containing two or more halogens in one molecule, such as methylene chloride, bis (chloromethyl) benzene, bis (chloromethyl) ether, etc. If reacted, the molecular weight can be increased, and if reacted with an organic halogen compound represented by the general formula 13, a hydrogenated polybutadiene polymer having a higher molecular weight and having an olefin group at the terminal can be obtained. .

  Specific examples of the organic halogen compound represented by the general formula (14) include, for example, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl). Examples include ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, and allyloxy (chloromethyl) benzene, but are not limited thereto. Of these, allyl chloride is preferable because it is inexpensive and easily reacts.

<< Epoxy Compound and / or Oxetane Compound (III) >>
In the curable composition of the present invention, an epoxy compound and / or an oxetane compound (III) can be added. These compounds can be cured by a photoacid generator or a photobase generator, and become a hybrid cured product with a vinyl polymer.

  The epoxy compound plays a role of lowering the viscosity of the curable composition to improve workability and improving the strength of the cured product.

  The epoxy compound may be any compound having an epoxy group, and examples thereof include bisphenol type epoxy resins and alicyclic epoxy resins.

  Specific examples of the bisphenol-type epoxy resin are not particularly limited, and known compounds can be used (for example, compounds described in paragraph [0174] of WO2007 / 029733).

  The hydrogenated type refers to a product obtained by hydrogen reducing a benzene ring part to a cyclohexyl ring.

  The alicyclic epoxy resin is typically a compound having a cyclohexene oxide group, a tricyclodecene oxide group, a cyclopentene oxide group, and the like. Specifically, a vinylcyclohexene diepoxide, a vinylcyclohexene monoepoxide, 3, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl 5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis ( 3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethylene) adipate, and the like are exemplified, but not limited thereto, and generally used epoxy resins can be used. These epoxy resins may be used alone or in combination of two or more.

  The epoxy compound preferably does not have an aromatic ring in order to absorb light and prevent curing or to be colored after curing.

  Among these epoxy resins, those having at least two epoxy groups in one molecule are preferable from the viewpoint of high reactivity and easy formation of a three-dimensional network upon curing.

  In order to obtain a transparent cured product when the mixture of the vinyl polymer of the present invention and the epoxy resin is cured, the epoxy resin is preferably compatible with the vinyl polymer. Hydrogenated bisphenol A type epoxy resins are easily compatible with various vinyl polymers, and easily obtain a transparent cured product.

  A curable composition having a combination of good compatibility between the vinyl polymer and the epoxy resin tends to take a modulation structure when cured, and as a result, a transparent cured product is easily obtained. Furthermore, the mechanical properties may be remarkably improved.

  For example, a combination of a vinyl polymer or vinyl copolymer whose main chain is more polar than butyl acrylate homopolymer and an epoxy resin having an aromatic ring, or a vinyl polymer or vinyl copolymer And a preferable combination such as a combination with an epoxy resin having no aromatic ring.

  Although it does not specifically limit as an example of the epoxy resin which does not have an aromatic ring, An alicyclic epoxy resin is preferable and the epoxy resin in which a glycidyl group is not directly attached to an alicyclic ring is more preferable.

The vinyl polymer or vinyl copolymer having a main chain having a polarity higher than that of the butyl acrylate homopolymer is not limited to this, but a preferred example is represented by the general formula (A) ′. A polymer or a copolymer.
− [CH ₂ —CR ^d (COOR ′)] _m − (A) ′
(In the formula, R is hydrogen or a methyl group, and R ′ is the same or different and is an alkoxyalkyl group or an alkyl group having 1 to 3 carbon atoms.)
Specifically, a copolymer of ethyl acrylate / butyl acrylate / acrylic acid 2-methoxyethyl (molar ratio 40-50 / 20-30 / 30-20) and bisphenol A type epoxy resin or bisphenol F type epoxy resin Preferred combinations include, but are not limited to, combinations of hydrogenated bisphenol A type epoxy resins and the like, and combinations of butyl acrylate homopolymer and hydrogenated bisphenol A type epoxy resins and hexahydrophthalic acid diglycidyl ester. It is not a thing.

  The oxetane compound plays a role of lowering the viscosity of the curable composition and improving workability and improving the strength of the cured product.

  Although there is no limitation in particular in an oxetane compound, The thing as described in WO2007 / 029733 paragraph [0185] is mentioned specifically.

The oxetane compound preferably does not have an aromatic ring in order to absorb light and inhibit curing, or to avoid coloring after curing.
Amount of addition of epoxy compound and / or oxetane compound (III) The amount of addition of epoxy compound and / or oxetane compound (III) is as follows: vinyl polymer (I) having at least one crosslinkable silyl group; The mixing ratio of the epoxy compound and / or the oxetane compound (III) is preferably in the range of 100/1 to 1/100 by weight, more preferably in the range of 100/5 to 5/100. Although it is more preferable that it is in the range of -10/100, it is not limited and can be set according to each application and purpose. Due to its characteristics, this curable composition can be used as an elastic adhesive for bonding materials with different linear expansion coefficients or for members that are repeatedly displaced by heat cycles, or when it becomes a transparent cured product. Taking advantage of its properties, it can be used as a coating agent in applications where the substrate is visible. For example, in this elastic adhesive application, if the mixing ratio of the epoxy resin is too large, the cured product becomes hard and the peel strength decreases, and if it is too small, the adhesive strength and water resistance decrease conversely. It is usually used in the range of about 10 to 150 parts by weight, preferably in the range of 20 to 100 parts by weight with respect to 100 parts by weight of the polymer (I).

<< Photoacid generator (II) >>
The photoacid generator (II) is an acid capable of crosslinking a crosslinkable silyl group by irradiating active energy rays such as visible light, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ rays and the like. A compound capable of releasing an active substance.

  The pKa of the acid generated by the photoacid generator is not limited, but is preferably less than about 3, more preferably less than about 1.

  The photoacid generator that can be used in the curable composition of the present invention is not particularly limited, and a known photoacid generator can be used (for example, JP 2000-1648 A, JP 2001-2001). 515533, WO 2002-83864, various compounds). Examples of the photoacid generator that can be preferably used in the present invention include sulfonate esters, onium salts, and carboxylic acid esters.

  More specifically, for example, sulfonic acid derivatives can be used (for example, compounds described in paragraphs [0190] to [0191] of WO2007 / 029733). Furthermore, not only one type of these compounds but also two or more types can be used in combination.

（Ｒ^２５はアルキルまたはフルオロアルキル基であり、Ｒ^２６は水素またはアルキル基であり、Ｒ^２７およびＲ^２８はアルキル基（同じであっても異なってもよい）であるか、または、環状構造の形成に協力する炭化水素含有基（例えばＲ^２７およびＲ^２８がそれらと結合している炭素と一緒にシクロヘキサン環を形成）である） In the present invention, sulfonate esters are particularly preferable. For example, a sulfonate ester represented by the following general structure can be used.

(R ²⁵ is an alkyl or fluoroalkyl group, R ²⁶ is hydrogen or an alkyl group, R ²⁷ and R ²⁸ are alkyl groups (which may be the same or different), or have a cyclic structure Hydrocarbon-containing groups that cooperate to form (eg, R ²⁷ and R ²⁸ together with the carbon to which they are attached form a cyclohexane ring)

（式中、Ｒ^２９はフルオロアルキル基であって、好ましくは２〜７個の炭素原子を有するペルフルオロアルキル基であり、Ｒ^３０〜Ｒ^３２は、アルキル基（同じであっても異なってもよい）であるか、または環状構造の形成に協力する炭化水素含有基（例えば、Ｒ^３０およびＲ^３１が、それらと結合している炭素原子と一緒にシクロヘキサン環を形成）である。） In the present invention, carboxylic acid esters can also be preferably used. For example, a carboxylic acid ester having the following structure can be used.

(Wherein R ²⁹ is a fluoroalkyl group, preferably a perfluoroalkyl group having 2 to 7 carbon atoms, and R ^{30 to} R ³² are alkyl groups (which may be the same or different). Or hydrocarbon-containing groups that cooperate in the formation of a cyclic structure (eg, R ³⁰ and R ³¹ together with the carbon atom to which they are attached form a cyclohexane ring).)

  In general, sulfonic acid esters and carboxylic acid esters require a heating step (50 ° C. to 100 ° C.) to liberate the acid.

In the present invention, an onium salt can be preferably used. Examples of the onium salts which can be used in the present invention, tetrafluoroborate _(BF 4 -), hexafluorophosphate _(PF 6 -), hexafluoroantimonate _(SbF 6 -), hexafluoroarsenate _(AsF 6 -), Hekisakuroru Antimonate (SbCl ₆ −), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO ₄ −), trifluoromethanesulfonate ion (CF ₃ SO ₃ −) , Sulfonium salts or iodonium having anions such as fluorosulfonate ion (FSO _3- ), toluenesulfonate ion, trinitrobenzenesulfonate anion, trinitrotoluenesulfonate anion Salt can be used.

  The sulfonium salt is not particularly limited, and a known one can be used (for example, a sulfonium salt described in paragraph [0199] of WO2007 / 029733). These can be used alone or in combination of two or more.

  The iodonium salt that can be used in the present invention is not particularly limited, and known ones can be used (for example, those described in paragraph [0200] of WO2007 / 029733). These can be used alone or in combination of two or more. As other onium salts, aromatic diazonium salts can be used. For example, p-methoxybenzenediazonium hexafluoroantimonate can be used.

Commercially available onium salts that can be used in the present invention include Sun Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI. -L160, SI-L110, SI-L147 (above, manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above, manufactured by Union Carbide), Adeka optomer SP-150, SP-151, SP-170, SP-171, SP-172 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624 , CI-2639, CI-2064 (above, manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-101 1, CD-1012 (manufactured by Sartomer), DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI -105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI-105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (above, manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (Nippon Kayaku Co., Ltd.), IBPF, IBCF (Sanwa Chemical ( Co., Ltd.) CD1012 (manufactured by Sartomer), IBPF, IBCF (above, manufactured by Sanwa Chemical Co., Ltd.), BBI-101, BBI-102, BBI-103, BBI-109 (above, manufactured by Midori Chemical Co., Ltd.) ), UVE1014 (manufactured by General Electronics Co., Ltd.) and the like.
Also described in J. Polymer Science: Part A: polymer Chemistry, Vol. 31, 1473-1482 (1993), J. Polymer Science: Part A: polymer Chemistry, Vol. 31, 1483-1491 (1993). Diaryliodonium salts that can be produced by the method can also be used.
When preparing a composition that uses the curable composition of the present application for an application that requires conductive properties, for example, a composition that can be applied with electrostatic assistance, (4-octyloxyphenyl) diphenylsulfonium tetrakis (3,5-bis -Trifluoromethylphenyl) borate, tris (dodecylphenyl) sulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, (4-octyloxyphenyl) It is preferable to use phenyliodonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, (tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate, and the like. Compositions using such salts can provide sufficient conductivity for static assisted paints, and can also be applied to electrostatic sprays, electric sprays, and continuous liquid applications using static assisted (e.g., roll coating, etc. And the like are suitable for application. When using such salts, generally no further conductivity enhancing agents are required, but they may be used with these preferred salts.

<< Photobase generator >>
The photobase generator is not particularly limited, and examples thereof include carbamates, amides, amines, imides, oxime esters, α-cobalt complexes, and imidazoles.
2-nitrobenzyl cyclohexyl carbamate, 1- (2-nitrophenyl) ethyl cyclohexyl carbamate, 2,6-dinitrobenzyl cyclohexyl carbamate, 1- (2,6-dinitrophenyl) ethyl cyclohexyl carbamate, 1- (3,5-dimethoxy Phenyl) -1-methylethyl cyclohexyl carbamate, 1-benzoyl-1-phenylmethyl cyclohexyl carbamate, 2-benzoyl-2-hydroxy-2-phenylethyl cyclohexyl carbamate, 1,2,3-benzenetriyl tris (cyclohexyl carbamate) , Α- (cyclohexylcarbamoyloxyimino) -α- (4-methoxyphenyl) acetonitrile, N- (cyclohexylcarbamoyloxy) succinimide, tri Phenylmethanol, o-carbamoylhydroxylamide, o-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaamminecobalt ( III) Tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, N- (2-nitrobenzyloxycarbonyl) imidazole, N- (3-nitrobenzyloxy) Carbonyl) Midazole, N- (4-nitrobenzyloxycarbonyl) imidazole, N- (4-chloro-2-nitrobenzyloxycarbonyl) imidazole, N- (5-methyl-2-nitrobenzyloxycarbonyl) imidazole, N- (4 , 5-dimethyl-2-nitrobenzyloxycarbonyl) imidazole, N- (2-methyl-2-phenylpropionyloxy) -N-cyclohexylamine, and the like.

  Among these, 2-nitrobenzyl, cyclohexyl carbamate, triphenylmethanol, o-carbamoylhydroxylamide, o-carbamoyloxime, [[(2,6-dinitrobenzyl) in terms of the balance between curability and storage stability during one-part formation. ) Oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaamminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -but Non, N- (2-nitrobenzyloxycarbonyl) imidazole, N- (3-nitrobenzyloxycarbonyl) imidazole, N- (4-nitrobenzyloxycarbonyl) imidazole, N- (4-chloro-2-nitrobenzyloxy) Carbonyl) imidazole, N- (5-methyl-2-nitrobenzyloxycarbonyl) imidazole, N- (4,5-dimethyl-2-nitrobenzyloxycarbonyl) imidazole and the like are preferable.

  Since the curable composition of the present invention uses a photoacid generator or a photobase generator, it is suitable for applications including a heat-sensitive substrate. Sensitizers can also be supplemented to promote acid or base release. The addition amount of the sensitizer is not particularly limited, but is preferably about 0.03 to about 0.1 parts by weight with respect to 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group. Examples of suitable sensitizers that can be used in the present invention include those described in Chapter 13 of Radiation Curing in Polymer Science and Technology, Volume 2, edited by Fouassier and Rabek, Elsevier SciencePubshers LTD, 1993. . 2-Isopropylthioxanthone is a particularly preferred sensitizer for use with di (dodecylphenyl) iodonium hexafluoroantimonate.

  The content of the photoacid generator or photobase generator in the curable composition of the present invention is not particularly limited, but from the viewpoint of curability, at least one crosslinkable silyl group is averaged at the terminal. The amount is preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the polymer (I), and more preferably 0.3 to 8.0 parts by weight from the viewpoint of the balance of physical properties of the cured product.

<< Compound having a carbon-carbon double bond having radical polymerizability >>
When the viscosity of the composition is increased, workability is remarkably reduced in all applications. Although it is not an essential component, it is not limited for the purpose of improving surface curability, imparting toughness, or improving workability by reducing viscosity, but it is a compound having a carbon-carbon double bond having radical polymerizability, that is, polymerization. It is preferable to add a functional monomer and / or oligomer.

  As the polymerizable monomer and / or oligomer, a monomer and / or oligomer having a radical polymerizable group or a monomer and / or oligomer having an anion polymerizable group is preferable from the viewpoint of curability.

  Examples of the radical polymerizable group include (meth) acryloyl group such as (meth) acryl group, styrene group, acrylonitrile group, vinyl ester group, N-vinylpyrrolidone group, acrylamide group, conjugated diene group, vinyl ketone group, and chloride. And vinyl group. Especially, what has the (meth) acryl group similar to the polymer used for this invention is preferable.

  Examples of the anionic polymerizable group include (meth) acryloyl groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, and vinyl ketone groups. Especially, what has the (meth) acryloyl type group similar to the polymer used for this invention is preferable.

  Specific examples of the monomer include (meth) acrylate monomer, cyclic acrylate, N-vinyl pyrrolidone, styrene monomer, acrylonitrile, N-vinyl pyrrolidone, acrylamide monomer, conjugated diene monomer, vinyl ketone monomer, polyfunctional monomer Etc.

  Examples of (meth) acrylate monomers include those described in paragraphs [0209] to [0216] of WO 2007/029733 as styrene monomers, styrene monomers, and polyfunctional monomers.

  As the oligomer, epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolak type epoxy acrylate resin, COOH group-modified epoxy acrylate type resin, polyol (polytetramethylene glycol, ethylene glycol and adipine) Acid polyester diol, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc. and organic isocyanate (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane) Diisocyanate, hexamethylene dii A urethane resin obtained from cyanate, xylylene diisocyanate, etc.) with a hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.} Urethane acrylate resin obtained by reaction, resin obtained by introducing a (meth) acryl group into the polyol via an ester bond, polyester acrylate resin, poly (meth) acryl acrylate resin (having a polymerizable reactive group) Poly (meth) acrylate resin) and the like.

  The number average molecular weight of the monomer and / or oligomer having a (meth) acryloyl group is preferably 5000 or less. Furthermore, in the case of using a monomer for improving the surface curability and reducing the viscosity for improving workability, it is more preferable that the molecular weight is 1000 or less because of good compatibility.

  The amount of the monomer and / or oligomer used is preferably 1 to 200 parts, more preferably 5 to 100 parts, per 100 parts of the vinyl polymer (I). When the curable composition of the present application further contains the component (III), the amount is preferably 1 to 200 parts, preferably 5 to 100 parts with respect to 100 parts in total of the vinyl polymer (I) and the component (III). Is more preferable. When the curable composition of the present application further contains component (III), the compound having a carbon-carbon double bond with respect to 100 parts by weight of the total of vinyl polymer (I) and component (III) is 1 to 200 parts by weight, preferably 5 to 100 parts by weight.

  As the organic solvent, those having a boiling point of 50 to 180 ° C. are usually preferable because of excellent workability during coating and drying before and after curing. Specifically, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol; methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, etc. Ester solvents; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; and cyclic ether solvents such as dioxane. These solvents may be used alone or in combination of two or more.

<< Vinyl polymer (IV) >>
It is also possible to add a vinyl polymer having an average of at least one crosslinkable acryloyl group at the terminal to the curable composition of the present invention.

<Functional group introduction method of vinyl polymer (IV)>
The method for producing such a vinyl polymer is not particularly limited. For example, a vinyl polymer having at least one highly reactive carbon-halogen bond is produced by the above-described method, and the reactive functional group ( It can be produced by converting to a substituent having a (meth) acryloyl group.
Below, the method to convert the terminal of the vinyl polymer which has a reactive functional group into group represented by General formula (2) is demonstrated.
—OC (O) C (R ^a ) ═CH ₂ (2)
The method for introducing the (meth) acryloyl group at the terminal of the vinyl polymer is not particularly limited, and examples thereof include the following methods.
A vinyl polymer having a halogen group (halogen atom) at its terminal, and the general formula (15):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (15)
(Wherein R ^a is a hydrogen atom or an organic group having 1 to 20 carbon atoms, M ⁺ is an alkali metal ion or 4
A method of reacting with a compound represented by the formula:
As a vinyl polymer having a halogen group at the terminal, the general formula (16):
-CR ³³ R ³⁴ X (16)
(In the formula, R ³³ and R ³⁴ are groups bonded to an ethylenically unsaturated group of a vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom).
Below, each said method is demonstrated in detail.

The introduction method is a method by a reaction between a vinyl polymer having a halogen group at the terminal and a compound represented by the general formula (15).
The vinyl polymer having a halogen group at the terminal is not particularly limited, but those having a terminal group represented by the general formula (16) are preferable.
Examples of the group bonded to the ethylenically unsaturated group of the vinyl monomer in R ³³ and R ³⁴ in the general formula (16) include a hydrogen atom, a methyl group, a carbonyl group, a carboxylate group, a toluyl group, a fluoro group, and a chloro group. , Trialkoxysilyl group, phenylsulfonic acid group, carboxylic acid imide group, cyano group and the like.
A vinyl polymer having a halogen group at the terminal, particularly a vinyl polymer having a terminal group represented by the general formula (16), is prepared by using the above-mentioned organic halide or sulfonyl halide compound as an initiator and catalyzing a transition metal complex. Is produced by a method of polymerizing a vinyl monomer, or a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, but the former is preferred.
There is no limitation in particular in the compound represented by General formula (15). Examples of the organic group having 1 to 20 carbon atoms in ^Ra in the general formula (15) are the same as those described above, and specific examples thereof are the same as those described above.
M ⁺ in the general formula (15) is a counter cation of an oxyanion, and examples of the type include alkali metal ions and quaternary ammonium ions.
Examples of the alkali metal ion include lithium ion, sodium ion, and potassium ion.
Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, dimethylpiperidinium ion, and the like. Of these, alkali metal ions are preferable, and sodium ions and potassium ions are more preferable.
The usage-amount of the compound shown by General formula (14) becomes like this. Preferably it is 1-5 equivalent with respect to the terminal group shown by General formula (15), More preferably, it is 1.0-1.2 equivalent.
The solvent for carrying out the reaction is not particularly limited, but a polar solvent is preferable because it is a nucleophilic substitution reaction. Amides, acetonitrile and the like are preferably used.
Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

<Photoradical polymerization initiator>
When the above-mentioned compound having a carbon-carbon double bond having radical polymerizability is added, it is preferable to add a photoradical polymerization initiator in order to photopolymerize the compound.

  Although there is no restriction | limiting in particular in radical photopolymerization initiator, For example, the thing of Unexamined-Japanese-Patent No. 2006-265488 Paragraph [0097] is mentioned, for example. Furthermore, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethylbenzoyl) -2,4,4- Examples thereof include acyl phosphine oxide photo radical initiators such as trimethyl-pentylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

  As the photo-radical polymerization initiator, 1-hydroxy-cyclohexyl-phenyl-ketone and 2-hydroxy-2-methyl-1-phenyl are preferable from the viewpoint of balance between curability and storage stability of the curable composition of the present invention. -Propan-1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-Dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are more preferable.

  The photoradical polymerization initiator may be used alone or in combination with other compounds. Specifically, combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combinations with iodonium salts such as diphenyliodonium chloride, and combinations with dyes and amines such as methylene blue, etc. can give.

  In addition, when using the said photoradical polymerization initiator, polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl catechol, can also be added as needed.

  Moreover, you may use a near-infrared light absorptive cationic dye as a near-infrared photoinitiator.

  Near-infrared light absorbing cationic dyes are excited by light energy in the region of 650 to 1500 nm, for example, near-infrared light disclosed in JP-A-3-111402, JP-A-5-194619, etc. It is preferable to use an absorbing cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer together.

  The amount of the photo-radical polymerization initiator added is not particularly limited because it is only necessary to slightly functionalize the system, but it is 0.001 to 10 parts with respect to 100 parts of the vinyl polymer (I). Is preferred.

<< trialkoxysilane compound or tetraalkoxysilane compound >>
Although not limited to the curable composition of the present invention, it is preferable to add a trialkoxysilane compound or a tetraalkoxysilane compound in order to improve the physical properties and storage stability of the cured product, and particularly preferably a trialkoxysilane. A compound. The trialkoxysilane compound or the tetraalkoxysilane compound may be represented by the formula R _4-n SiY ′ _n (where Y ′ is a hydrolyzable group, R is an organic group and may or may not contain a functional group). n is 3 or 4), and specific examples thereof include those described in WO 2007/029733, paragraph [0228]. Or these partial hydrolysis-condensation products etc. are mentioned. One or more of these can be used in combination.

  The amount of trialkoxysilane compound or tetraalkoxysilane compound used is 0.1 to 30 parts by weight, preferably 0.3 to 20 parts by weight, more preferably 0.5 to 100 parts by weight based on 100 parts by weight of the vinyl polymer. 10 parts by weight.

  The trialkoxysilane compound or the tetraalkoxysilane compound is preferably added after the curable composition is in an anhydrous state, but it may be added while still containing moisture. .

<< Curable composition >>
In the curable composition of the present invention, various compounding agents may be added according to the intended physical properties.

<Curing catalyst and curing agent>
In the present invention, the vinyl polymer having a crosslinkable silyl group can be cured by a photoacid generator or a photobase generator, but in addition thereto, various conventionally known condensation catalysts may be added. However, when preparing a one-component formulation to which these are added, it is necessary to sufficiently remove moisture from the composition.

  Examples of such a condensation catalyst include those described in WO 2007/029733, paragraphs [0231] to [0232].

  These catalysts may be used alone or in combination of two or more. The blending amount of the condensation catalyst is preferably about 0.01 to 20 parts, more preferably 0.5 to 5 parts, with respect to 100 parts (parts by weight, hereinafter the same) of the polymer having a crosslinkable silyl group. 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 addition, although it does not specifically limit, a preferable result is given by the point that a tin-type curing catalyst tends to control sclerosis | hardenability.

  Although not particularly limited, when a one-component composition as described below is used, tetravalent tin is preferable in the case of a tin-based curing catalyst from the viewpoints of curing speed and storage stability of the composition. Combinations of valent tin and organic amines and non-tin compounds can also be used.

  In addition, although not particularly limited, when used for applications such as a sealing agent for siding board, it is easy to relieve the stress of the cured product, regardless of whether it is a one-component or two-component system. Tetravalent tin is preferred from the standpoint that there is no peeling at the adhesive interface.

  In recent years, the focus has been on environmental issues, and tin-based catalysts may be disliked. In such cases, other non-tin-based catalysts such as bismuth carboxylate and titanium carboxylate may be selected.

  Further, in the curable composition of the present invention, in order to further enhance the activity of the condensation catalyst, it is also possible to use the above-mentioned silane coupling agent having an amino group as a cocatalyst in the same manner as the amine compound. . The amino group-containing silane coupling agent is a compound having a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as a hydrolyzable silyl group) and an amino group, and the groups already exemplified as the hydrolyzable group. A methoxy group, an ethoxy group, and the like are preferable from the viewpoint of hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly 3 or more.

  The compounding amount of these amine compounds is preferably about 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group. If the compounding amount of the amine compound is less than 0.01 parts by weight, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, when the compounding amount of the amine compound exceeds 30 parts by weight, the pot life may become too short, which is not preferable from the viewpoint of workability.

  These amine compounds may be used alone or in combination of two or more.

  Furthermore, a silicon compound having no amino group or silanol group may be added as a promoter. These silicon compounds are not limited, but phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane and the like are preferable. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are most preferable because of low cost and easy availability.

  The amount of the silicon compound is preferably about 0.01 to 20 parts, more preferably 0.1 to 10 parts, based on 100 parts of the polymer having a crosslinkable silyl group. 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.

  The type and amount of the curing catalyst / curing agent can control the curability and mechanical properties of the present invention according to the purpose and application. Also, the type and amount of the curing catalyst / curing agent can be changed depending on the reactivity of the silyl group of the polymer having a crosslinkable silyl group. If the reactivity is high, a small amount of 0.01 to 1 part It is possible to sufficiently cure within the range.

  The type and addition amount of the curing catalyst / curing agent can be selected according to the type of Y and the number of a in the vinyl polymer of the present invention. The curability and mechanical properties of the present invention are selected according to the purpose and application. Etc. can be controlled. When Y is an alkoxy group, the smaller the number of carbon atoms, the higher the reactivity, and the higher the number a, the higher the reactivity, so that it can be sufficiently cured in a small amount.

<Dehydrating agent>
The curable composition increases in viscosity and gelation during storage due to moisture at the time of production, etc., causing difficulty in workability during use, By using the advanced curable composition, the physical properties of the cured product after curing may be deteriorated, resulting in a problem that the original sealing property and the like are impaired. That is, the storage stability of the curable composition may be a problem.

  In order to improve the storage stability of this curable composition, there is a method of reducing the moisture content of the curable composition by azeotropic dehydration. For example, about 0.1 to 10 parts by weight of a volatile organic compound having a minimum azeotropic point with respect to water is added and mixed uniformly, and then heated to about 50 to 90 ° C. and sucked with a vacuum pump. A method of removing an azeotropic composition of a compound into a body is mentioned. Volatile organic compounds having a minimum azeotropic point with respect to water include halides such as methylene chloride, chloroform, carbon tetrachloride, and trichloroethylene; alcohols such as ethanol, allyl alcohol, 1-propanol, and butanol; ethyl acetate, propionic acid Examples thereof include esters such as methyl; ketones such as methyl ethyl ketone and 3-methyl-2-butanone; ethers such as ethyl ether and isopropyl ether; hydrocarbons such as benzene, toluene, xylene and hexane. However, since this method involves a devolatilization operation, it is necessary to devise other volatile compounding agents, or it is necessary to treat, recover, etc., the volatile organic compound to be azeotroped. Therefore, it may be preferable to add the following dehydrating agents.

  As described above, a dehydrating agent for removing moisture in the composition can be added to the composition of the present invention for the purpose of improving storage stability. Examples of the dehydrating agent include inorganic solids such as phosphorus pentoxide, sodium hydrogen carbonate, sodium sulfate (anhydrous bow glass), and molecular sieves. These solid dehydrating agents may be used, but the liquidity after addition tends to be acidic or basic, condensing easily, resulting in poor storage stability and workability such as removing the solid later. In some cases, the liquid hydrolyzable ester compound described below is preferable. Examples of hydrolyzable ester compounds include trialkyl orthoformate such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate. And trialkyl orthoacetate such as tributyl orthoacetate, and those selected from the group consisting of these compounds.

The amount of the dehydrating agent used is not limited, but is 0.1 to 30 parts by weight, preferably 0.3 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the vinyl polymer. Part.
In addition, when adding these dehydrating agents, it is preferable to carry out after making a curable composition anhydrous, but you may add in the state containing moisture.

<Adhesive agent>
To the composition of the present invention, an aminosilane compound, other silane coupling agents, and an adhesion-imparting agent other than silane coupling agents can be added. 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 silane coupling agents include amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, halogen and other functional groups such as halogens. Specific examples thereof Examples thereof include those described in WO2007 / 029733, paragraph [0249].

  The silane coupling agent used for this invention is normally used in 0.1-20 parts with respect to 100 parts of polymers which have a crosslinkable silyl group. In particular, it is preferably used in the range of 0.5 to 10 parts. 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. Moreover, if the usage-amount is about 1 part with respect to 100 parts of polymers which have a crosslinkable silyl group, it will hardly affect transparency of hardened | cured material.

  Specific examples other than the silane coupling agent are not particularly limited. For example, epoxy resin, phenol resin, polystyrene-polybutadiene-polystyrene, polystyrene-polyisoprene-polystyrene, polystyrene-polyisoprene / butadiene copolymer-polystyrene, polystyrene. -Polyethylene / propylene copolymer-Polystyrene, polystyrene-polyethylene / butylene copolymer-Linear or branched block copolymers such as polystyrene, polystyrene-polyisobutene-polystyrene, alkyl sulfonates, sulfur, alkyl titanates And aromatic polyisocyanate. The epoxy resin can be used by reacting with the above amino group-containing silanes.

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

  The type and amount of the adhesion-imparting agent can be selected according to the type of Y and the number of a in the vinyl polymer of the present invention, and the curability and mechanical properties of the present invention depending on the purpose and application Can be controlled. In particular, care must be taken in selecting it because it affects curability and elongation.

<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 example, what is described in WO2007 / 029733 paragraph [0252] is mentioned by the objectives, such as adjustment of a physical property and adjustment of a property.

  In particular, a polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15,000 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 are obtained. Mechanical properties such as strength and elongation can be adjusted, and the initial physical properties are maintained over a long period of time compared to the case of using a low molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule. It is possible to improve the drying property (also referred to as paintability) when an alkyd paint is applied. 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 to 15,000 above, it is preferably 800 to 10,000, and more preferably 1,000 to 8,000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen.

  Among these polymer plasticizers, polyether plasticizers and (meth) acrylic polymer plasticizers are preferable from the viewpoint of high elongation characteristics or high weather resistance. Examples of the synthesis method of 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 particularly limited to, for example, ARUFON UP series (UP-1000, UP-1110, UP-2000, UP-2130) (referred to as SGO) of Toagosei Co., Ltd. (waterproof journal, June 2002 issue) reference). 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 from the viewpoint of viscosity, and 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.

  From the viewpoint of viscosity, it is preferable to have a branched structure in the main chain because the viscosity becomes lower at the same molecular weight. The high temperature continuous polymerization method mentioned above is mentioned as this example.

  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. In addition, for example, in the case of a composition in which the vinyl polymer of the present invention and a polyether polymer which is one of optional polymers having a crosslinkable functional group are mixed, from the point of compatibility of the mixture Phthalic acid esters and acrylic polymers are particularly preferred.

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

  The amount of the plasticizer used is not limited, but is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the polymer having a crosslinkable silyl group. It is. If the amount is less than 5 parts by weight, the effect as a plasticizer is hardly exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product tends to be insufficient.

<Filler>
In the curable composition of the present invention, various fillers may be used as needed within a range not hindering curing by active energy rays. Although it does not specifically limit as a filler, The thing as described in WO2007 / 029733 paragraph [0261] is mentioned.

  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 it is desired to obtain a cured product having high transparency or strength in order to facilitate curing by active energy rays, fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, carbon black, A filler selected from surface-treated fine calcium carbonate, crystalline silica, fused silica, calcined clay, clay and activated zinc white can be added. These are suitable for transparent architectural sealants, transparent DIY adhesives and the like. Among them, the specific surface area (according to BET adsorption method) of ^{10 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 is previously hydrophobically treated with an organosilicon compound such as organosilane, organosilazane, diorganocyclopolysiloxane, or the like is more preferable.

  More specific examples of silica-based fillers with high reinforcing properties are not particularly limited, but are those of Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Silica Corporation, which is one of precipitated silica. Nipsil etc. are mentioned. Silica having an average particle diameter of 1 nm to 30 μm can be used. Particularly for fumed silica, it is more preferable to use fumed silica having an average primary particle diameter of 1 nm to 50 nm because the reinforcing effect is particularly high. In addition, the average particle diameter in this invention is based on the sieving method. Specifically, the powder is classified with various sieves (micro sieves, etc.), and the value corresponding to the sieve openings through which 50% by weight of the total weight of the powder used for measurement has passed (weight average) Particle size). A composition reinforced with a filler is excellent in immediate fixability and suitable for automobile glass glazing adhesion.

  Transparency can also be obtained by using a resin powder such as PMMA powder as a filler.

  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. As the shape of calcium carbonate, various shapes such as a cubic non-cubic shape and an irregular shape can be used.

  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 those described in paragraph [0267] of WO2007 / 029733. 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 crushing 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 a product having various average particle diameters 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 lowered or when the purpose is to increase the viscosity only.

  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, when heavy calcium carbonate and colloidal calcium carbonate having a specific surface area of 1.5 m ² / g or more are combined as necessary, the increase in the viscosity of the compound is moderately suppressed, and a cured product is obtained. The effect of improving the breaking strength, breaking elongation, adhesiveness, and weather resistance can be greatly expected.

  When the filler is used, the addition amount is preferably 5 to 1,000 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group, and preferably 20 to 500 parts by weight. More preferably, it is used in a range of 40 to 300 parts by weight. When the blending amount is less than 5 parts by weight, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient, and when it exceeds 1,000 parts by weight, the curable composition Workability may be reduced. A filler may be used independently and may be used together 2 or more types.

  It should be noted that dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like may be added in a large amount, thereby hindering the transparency of the present invention and resulting in an opaque cured product.

<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 as described in “the latest technology of functional filler” (CMC), the diameter is 1 mm or less, preferably 500 μm or less, and more preferably 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 more preferably to use a micro hollow body having a specific gravity of 0.5 g / cm ³ or less.

  Specific examples of the upper balloon include those described in WO 2007/029733, paragraphs [0276] to [0278].

  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 designed to improve workability such as cutting properties before curing the composition, reduce costs by reducing weight without losing flexibility and elongation / strength after curing, and further design such as surface matting and sputtering. Used for imparting sex.

Although content of a balloon is not specifically limited, Preferably it is 0.1-50 parts with respect to 100 weight part of polymers which have a crosslinkable silyl group, More preferably, it can use in 0.1-30 parts. If this amount is less than 0.1 part, the effect of reducing the weight is small, and if it is 50 parts 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, more preferably 5 to 30 parts are preferred.
<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 modifier, For example, the thing as described in WO2007 / 029733 paragraph [0281] is mentioned. 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.

<Silanol-containing compound>
You may add a silanol containing compound to the curable composition of this invention as needed, such as changing the physical property of hardened | cured material. The silanol-containing compound refers to a compound having one silanol group in the molecule and / or a compound capable of producing a compound having one silanol group in the molecule by reacting with moisture. Only one of these may be used, or both compounds may be used simultaneously.

The compound having one silanol group in the molecule, which is one of the silanol-containing compounds, is not particularly limited, and examples thereof include those described in paragraphs [0282] to [0291] of WO2007 / 029733.
Examples thereof include compounds in which a main chain is composed of silicon, carbon, oxygen, and a silanol group bonded to a polymer terminal. Among these, (CH ₃ ) ₃ SiOH, which is easy to obtain and has a low molecular weight, is preferable from the viewpoint of effects.

The compound having one silanol group in the molecule reacts with a crosslinkable silyl group of a polymer having a crosslinkable silyl group or a siloxane bond formed by crosslinking, thereby reducing the number of crosslinking points and curing. It gives a composition having flexibility and low surface tack and excellent dust resistance.
Moreover, the compound which can produce | generate the compound which has one silanol group in a molecule | numerator by reacting with a water | moisture content which is one of the components of this invention is not specifically limited,
Although those described in paragraphs [0293] to [0294] of WO2007 / 029733 can be suitably used, (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ is particularly preferred from the amount of silanol groups contained in the hydrolysis product.

Furthermore, the compound that can form a compound having one silanol group in the molecule by reacting with moisture, which is one of the components of the present invention, is not particularly limited. ) Is preferred.
((R ⁵⁸ ) ₃ SiO) _n R ⁵⁹ (16)
(In the formula, R ⁵⁸ is the same as described above. N represents a positive number, and R ⁵⁹ represents a group obtained by removing a part or all of the active hydrogen from the active hydrogen-containing compound.)
^R58 is preferably a methyl group, an ethyl group, a vinyl group, a t-butyl group, or a phenyl group, and more preferably a methyl group.
The (R ⁵⁸ ) ₃ Si group is particularly preferably a trimethylsilyl group in which all three R ⁵⁸ are methyl groups. N is preferably 1 to 5.

The active hydrogen-containing compound from which R ⁵⁹ is derived is not particularly limited.
Methanol, ethanol, n-butanol, i-butanol, t-butanol, n-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propanediol, tetra Alcohols such as methylene glycol, polytetramethylene glycol, glycerin, trimethylolpropane, pentaerythritol; phenols such as phenol, cresol, bisphenol A, hydroquinone; formic acid, acetic acid, propionic acid, lauric acid, palmitic acid, stearic acid, Behenic acid, acrylic acid, methacrylic acid, oleic acid, linoleic acid, linolenic acid, sorbic acid, oxalic acid, malonic acid, kocha Carboxylic acids such as acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid; ammonia; amines such as methylamine, dimethylamine, ethylamine, diethylamine, n-butylamine, imidazole; acetamide, benzamide Acid amides such as urea, ureas such as urea and N, N′-diphenylurea, and ketones such as acetone, acetylacetone and 2,4-heptadione.

Compounds capable of producing a compound having one silanol group in the molecule by reacting with the water represented by the general formula (16) are, for example, trimethylsilyl chloride and dimethyl (t It can be obtained by reacting a compound having a group capable of reacting with active hydrogen such as a halogen group together with a (R ⁵⁸ ) ₃ Si group, which is also called a silylating agent such as -butyl) chloride, but is not limited thereto. (However, R ⁵⁸ is the same as described above.)

When the compound represented by the general formula (16) is specifically exemplified,
Although what is described in WO2007 / 029733 paragraph [0299] is mentioned, it is not limited to these. These may be used alone or in combination of two or more.

Further, a compound that can be represented by the general formula (((R ⁶⁰ ) ₃ SiO) (R ⁶¹ O) _s ) _t Z, CH ₃ O (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ ,
_{CH 2 = CHCH 2 (CH 2} CH (CH 3) O) 5 Si (CH 3) 3,
(CH ₃ ) ₃ SiO (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO (CH ₂ CH (CH ₃ ) O) ₇ Si (CH ₃ ) ₃
(In the formula, R ⁶⁰ is the same or different substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom, R ⁶¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and s and t are positive integers. , S is 1 to 6, s × t is 5 or more, Z is a 1 to 6-valent organic group)
Etc. can also be used suitably. These may be used alone or in combination of two or more.

  Among the compounds that can produce a compound having one silanol group in the molecule by reacting with moisture, the active hydrogen compound produced after hydrolysis is not adversely affecting storage stability, weather resistance, etc. Phenols, acid amides and alcohols are preferred, and phenols and alcohols whose active hydrogen compounds are hydroxyl groups are more preferred.

  Among the above compounds, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, trimethylsilylphenoxide, trimethylsilylated product of n-octanol, trimethylsilylated product of 2-ethylhexanol, tris (trimethylsilyl) ated product of glycerin, A tris (trimethylsilyl) product of trimethylolpropane, a tris (trimethylsilyl) product of pentaerythritol, a tetra (trimethylsilyl) product of pentaerythritol and the like are preferable.

  A compound that can generate a compound having one silanol group in the molecule by reacting with moisture has one silanol group in the molecule by reacting with moisture during storage, curing or after curing. A compound is produced. The compound having one silanol group in the molecule thus produced reacts with the crosslinkable silyl group of the vinyl polymer or the siloxane bond formed by crosslinking as described above, thereby reducing the number of crosslinking points. It is presumed that it is reduced and the cured product is given flexibility.

  The structure of the silanol-containing compound can be selected depending on the type of Y and the number of a in the vinyl polymer of the present invention, and controls the curability and mechanical properties of the present invention according to the purpose and application. It is possible.

  The silanol-containing compound may be used in combination with an air oxidation curable material described later, and by using it together, the modulus of the cured product is kept low, and the curability and dust adhesion of the alkyd paint coated on the surface are improved. Therefore, it is preferable.

  The addition amount of the silanol-containing compound can be appropriately adjusted according to the expected physical properties of the cured product. The silanol-containing compound can be added in an amount of 0.1 to 50 parts by weight, preferably 0.3 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group. If the amount is less than 0.1 parts by weight, the effect of addition does not appear. If the amount exceeds 50 parts by weight, the crosslinking becomes insufficient, and the strength and gel fraction of the cured product are too low.

Moreover, the time which adds a silanol containing compound is not specifically limited, You may add at the time of manufacture of a polymer, and you may add at the time of preparation of a curable composition.
<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.

  A thixotropic agent (anti-sagging agent) is also called a thixotropic agent. Thixotropy imparts fluidity when a strong force is applied, such as when extruding from a cartridge into a bead, applying with a spatula, or spraying with a spray, etc., until it hardens after application or construction. It imparts the property of not flowing down.

  The thixotropy imparting agent (anti-sagging agent) is not particularly limited, and examples thereof include amide waxes, hydrogenated castor oil, hydrogenated castor oil derivatives, fatty acid derivatives, Metal soap such as calcium phosphate, aluminum stearate, barium stearate, organic compounds such as 1,3,5-tris (trialkoxysilylalkyl) isocyanurate, calcium carbonate and fine powder surface-treated with fatty acids and resin acids Examples thereof include inorganic compounds such as silica and carbon black.

  Fine powder silica means a natural or artificial inorganic filler mainly composed of silicon dioxide. Specific examples include kaolin, clay, activated clay, silica sand, silica stone, diatomaceous earth, anhydrous aluminum silicate, hydrous magnesium silicate, talc, perlite, white carbon, mica fine powder, bentonite, and organic bentonite. it can.

Among these, ultrafine anhydrous silica or organic bentonite produced by reacting a volatile compound containing silicon in the gas phase is preferable. At least ^{50 m} 2 / g, and more preferably it has a specific surface area of 50 to 400 m ² / g. Either hydrophilic silica or hydrophobic silica can be used. Hydrophobic silica whose surface is hydrophobically treated with silazane, chlorosilane, alkoxysilane, or polysiloxane having only a methyl group as an organic substituent bonded to a silicon atom is preferable. .

  Specific examples of the surface treatment agent include silazanes such as hexamethyldisilazane; halogenated silanes such as trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane; trimethylalkoxysilane and dimethyldialkoxysilane. Alkoxysilanes such as methyltrialkoxysilane (wherein the alkoxy group includes methoxy, ethoxy, propoxy, butoxy, etc.); cyclic or linear polydimethylsiloxane, etc. Examples thereof include siloxanes, and these may be used alone or in combination of two or more. Among these, hydrophobic fine powder silica subjected to surface treatment with siloxanes (dimethylsilicone oil) is preferable from the viewpoint of thixotropic effect.

  Moreover, thixotropy is increased when a polyether compound such as diethylene glycol, triethylene glycol, or polyethylene glycol, a reaction product of a polyether compound and a functional silane, or a nonionic surfactant having an ethylene oxide chain is used in combination with fine powder silica. . These nonionic surfactants may be used alone or in combination of two or more.

  Specific examples of the fine powder silica include, for example, trade names Aerosil R974, R972, R972V, R972CF, R805, R812, R812S, RY200, RX200, RY200S, # 130, # 200, # 300, R202, etc., manufactured by Nippon Aerosil. And trade name Nippon Sil SS series made by Nippon Silica, trade names Rheorosil MT-10, MT-30, QS-102, QS-103, made by Soda Tokuyama, trade names made by Cabot, Cabosil TS-720, MS-5, MS -7, commercial products such as Sven and Organite manufactured by Toyoshiro Yoko.

  The organic bentonite is a powdery substance obtained by finely pulverizing montmorillonite ore, which is surface-treated with various organic substances. Examples of the organic compound include aliphatic primary amines and aliphatic quaternary amines (all of which preferably have 20 or less carbon atoms). Specific examples of the organic bentonite include, for example, trade names Orven D, New D Orven, manufactured by Shiraishi Kogyo, trade name Hard Sil, manufactured by Kaoru Tsuchiya, clay # 30 manufactured by Bergess Pigment, Southern Cray # 33, manufactured by National Lead, USA. “Bentone 34” (dimethyloctadecyl ammonium bentonite) and the like.

  The thixotropic index means a ratio of apparent viscosity at a low rotation speed (for example, 0.5 to 12 rpm) and a high speed (for example, 2.5 to 60 rpm) in viscosity measurement using a rotational viscometer (however, The ratio of the high speed rotation speed to the low speed rotation speed is preferably at least 5 and more preferably in the range of 5-10.

These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more.
<Photo-curing substance>
You may add a photocurable substance to the curable composition of this invention as needed. The photo-curing substance is a substance in which the molecular structure undergoes a chemical change in a short time due to the action of light, resulting in a change in physical properties such as curing. By adding this photocurable substance, the tackiness (also referred to as residual tack) of the cured product surface when the curable composition is cured can be reduced. This photo-curing substance is a substance that can be cured by exposure to light, but a typical photo-curing substance should be allowed to stand at room temperature for one day, for example, in a room 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 or azide resins, epoxy compounds, vinyl ether compounds, and the like.

  The unsaturated acrylic compound is not particularly limited, and known compounds can be used (for example, compounds described in paragraphs [0317] to [0318] of WO2007 / 029733).

  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.

  Examples of the epoxy compound and vinyl ether compound include epoxy group-terminated or vinyl ether group-terminated polyisobutylene.

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

  The photocurable material is preferably added in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group. If the amount is less than 0.01 parts by weight, the effect is small. If the amount exceeds 20 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 oxidative curable substance can be cured by, for example, standing in air indoors for 1 day.

  The air oxidation curable substance is not particularly limited, and known substances can be used (for example, those described in paragraph [0324] of WO2007 / 029733). 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 may be used in combination with the above-described photocurable substance, and further, the above-mentioned silanol-containing compound may be used in combination. Combined use of these two components or combination of the three components further demonstrates its effect, especially when exposed to a long period of time, and in a severely contaminated area with a lot of dust and fine earth and sand. This is particularly preferable.

  The air oxidation curable substance is preferably added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polymer having a crosslinkable silyl group. If the amount is less than 0.01 parts by weight, the effect is small. If the amount exceeds 20 parts by weight, the physical properties may be adversely affected.

<Antioxidant>
You may add antioxidant to the curable composition of this invention as needed. Various types of antioxidants are known, and are described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242), issued by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these. For example, phosphoethers such as thioethers such as MARK PEP-36 and MARK AO-23 (all manufactured by Asahi Denka Kogyo), Irgafos 38, Irgafos 168, Irgafos P-EPQ (all manufactured by Ciba Specialty Chemicals) An inhibitor etc. are mentioned. Of these, hindered phenol compounds as shown below are preferred.

  Specific examples of the hindered phenol compound include the following. Although the thing of WO2007 / 029733 gazette [0329]-[0330] can be illustrated, it is not limited to these.

  Antioxidants may be used in combination with the light stabilizers described later, and are particularly preferred because they can further exert their effects and improve heat resistance in particular. 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.

  It is preferable that the usage-amount of antioxidant is the range of 0.1-10 weight part with respect to 100 weight part of polymers which have a crosslinkable silyl group. If it is less than 0.1 parts by weight, the effect of improving the weather resistance is small, and if it exceeds 10 parts by weight, there is no great difference in the effect, which is economically disadvantageous.

<Light resistance stabilizer>
You may add a light-resistant stabilizer to the curable composition of this invention as needed. Various types of light-resistant stabilizers are known, and are described in, for example, “Antioxidant Handbook” issued by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242), issued by CM Chemical Co., Ltd. There are various types. Although not necessarily limited to these, among the light-resistant stabilizers, ultraviolet absorbers and hindered amine light stabilizer compounds are preferred. Specific examples include those described in WO 2007/029733, paragraphs [0332] to [0334].
However, the present invention is not limited to the above-described compounds.

  The light-resistant stabilizer may be used in combination with the above-mentioned antioxidant, and is particularly preferable because the effect is further exhibited by using it together, and the weather resistance may be improved. The combination is not particularly limited, but a combination of the above-mentioned hindered phenolic antioxidant and, for example, a benzotriazole-based ultraviolet absorber or a combination of the above-mentioned hindered phenolic antioxidant and a hindered amine light stabilizer compound is preferable. . Or the combination of the above-mentioned hindered phenolic antioxidant, for example, a benzotriazole type ultraviolet absorber and a hindered amine light stabilizer compound is preferable. Tinuvin C353, Tinuvin B75 (both manufactured by Ciba Specialty Chemicals) and the like in which a light stabilizer and an antioxidant are mixed in advance may be used.

  The hindered amine light stabilizer may be used in combination with the above-mentioned photo-curing substance, and it is particularly preferable because the hindered amine light stabilizer further exerts its effect and particularly the weather resistance may be improved. The combination is not particularly limited, but in this case, a hindered amine light stabilizer containing a tertiary amine is preferable because the viscosity increase during storage is small and the storage stability is good.

  It is preferable that the usage-amount of a light stabilizer is the range of 0.1-10 weight part with respect to 100 weight part of polymers which have a crosslinkable silyl group. If it is less than 0.1 parts by weight, the effect of improving the weather resistance is small, and if it exceeds 10 parts by weight, there is no great difference in the effect, which is economically disadvantageous.

<Compatibilizer>
A compatibilizing agent can be added to the curable composition of the present invention. As a specific example of such an additive, for example, a copolymer of a plurality of vinyl monomers described in the specification of JP-A-2001-329025 can be used.

<Compound having an α, β diol structure or an α, γ diol structure in the molecule>
A compound having an α, β diol structure or an α, γ diol structure may be added to the molecule contained in the curable composition of the present invention. As the compound having an α, β diol structure or an α, γ diol structure, generally well-known compounds can be used. In the present specification, the α, β diol structure represents a structure having two hydroxyl groups at adjacent carbon atoms, and the α, γ diol structure has two hydroxyl groups at adjacent carbon atoms. In addition, as represented by glycerin and the like, both α and β diol structures and α and γ diol structures, or polyols such as triols and tetraols containing either structure are also included.

  The compound having an α, β diol structure or an α, γ diol structure in the molecule is not particularly limited, and examples thereof include those described in paragraphs [0337] to [0338] of WO2007 / 029733.

  Many of the above-mentioned compounds are easily used as emulsifiers, surfactants, dispersants, antifoaming agents, antifogging agents, solubilizers, thickeners, and lubricants.

  The above compounds may be used alone or in combination of two or more. The amount of the compound used is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the vinyl polymer (I). If the amount is less than 0.01 parts by weight, the intended effect cannot be obtained. If the amount exceeds 100 parts by weight, the mechanical strength of the cured product is insufficient, which is not preferable. More preferably, it is 0.1-20 weight part.

<Other additives>
Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include flame retardants, curability modifiers, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents and the like. 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.

  The curable composition of the present invention can be used substantially without a solvent. Although a solvent may be used from the viewpoint of workability and the like, it is desirable not to use it because of environmental influences.

<< Form of formulation >>
Although the curable composition of the present invention is not particularly limited, it may be prepared as a one-component type in which all the blending components are blended and stored in advance, and the vinyl polymer (I) and the photoacid generator or photobase The generator (II) and other curing agents / curing catalysts may be separately provided and adjusted as a two-component type in which the compounding material is mixed before use. As described above, the general one-component polymer having a crosslinkable silyl group requires sufficient physical and chemical dehydration. However, in the case of the composition of the present invention, a photoacid generator is used. Alternatively, since the photobase generator does not act as a curing catalyst until light irradiation, there is a case where strict dehydration is not necessary.

<< Curing method >>
The curable composition of the present invention can be cured by irradiation with active energy rays. The active energy ray source is not particularly limited, but depending on the nature of the photopolymerization initiator, for example, irradiation of light and electron beam by a high pressure mercury lamp, low pressure mercury lamp, electron beam irradiation device, halogen lamp, light emitting diode, semiconductor laser, etc. Is given.

<< Brake fluid, antifreeze fluid >>
The “non-mineral brake fluid for automobiles defined in JIS K 2233” in the present invention is a medium for obtaining the braking force by transmitting the depression force of the brake pedal to the disc rotor through the brake cylinder. Ingredients are broadly classified into glycol and silicone.
The “antifreeze liquid defined in JIS K 2234” is an antifreeze liquid mainly composed of ethylene glycol used for preventing freezing of the cooling liquid for a liquid-cooled internal combustion engine and preventing corrosion of the cooling mechanism.

<< Dip test method >>
Furthermore, the “immersion test of JIS K 6258” means that the entire surface of the cured vinyl polymer is immersed in the non-mineral brake fluid or antifreeze for automobiles, and the mass and volume before and after immersion. Etc. are measured.
In the above immersion test, the cured product obtained by curing the curable composition of the present invention has a mass change rate before and after immersion of 50% or less, preferably based on the original mass and volume before immersion. Is 30% or less, more preferably 20% or less.
Moreover, the volume change rate before and after immersion is 50% or less, preferably 30% or less, more preferably 20% or less.

<< Evaluation method after immersion test >>
As a physical property evaluation of the cured product after immersion in brake fluid or antifreeze solution, there is mechanical strength evaluation. “The tensile property of JIS K 6251” is a method of measuring the elongation and strength of a dumbbell-shaped cured product using a tensile tester such as an autograph. At that time, the rate of change in elongation before and after immersion is 50% or less, preferably 30% or less, more preferably less than 20%.

<< Usage >>
The curable composition of the present invention includes, but is not limited to, an elastic sealant for construction, a sealant for siding boards, a sealant for double glazing, a sealant for vehicles, such as an architectural and industrial sealant, and a back surface of a solar cell Electrical and electronic parts materials such as sealants, electrical insulation materials such as insulation coatings for electric wires and cables, adhesives, adhesives, elastic adhesives, contact adhesives, tile adhesives, reactive hot melt adhesives, Paints, powder paints, coating materials, foams, sealing materials such as can lids, heat dissipation sheets, electrical and electronic potting agents, films, gaskets, marine deck caulking, casting materials, various molding materials, artificial marble, and nets Sealing material for rust prevention and waterproofing of glass and laminated glass end faces (cut parts), vibration proofing, vibration control, soundproofing and seismic isolation materials used in automobiles, ships, home appliances, Dosha parts, electrical parts, various machine parts liquid sealing material used in such, are available in a variety of applications such as waterproofing agents.

  Furthermore, the molded product showing rubber elasticity, which is a cured product obtained from the curable composition of the present invention, can be widely used mainly in 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 them, the curable composition of the present invention is useful as an adhesive / adhesive composition, particularly useful as a sealant, an adhesive, a pressure-sensitive adhesive, a potting agent, and a coating agent, and particularly requires weather resistance and heat resistance. It is also useful for applications where transparency is required. 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.

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 synthesis examples, examples and comparative examples, “part” and “%” represent “part by weight” and “% by weight”, respectively.

  Synthesis examples of the polymer in the present invention are shown below.

In the following synthesis 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 filled with polystyrene cross-linked gel (shodex GPC K-804, K-802.5; Showa Denko) and chloroform as a GPC solvent were used.
In the following examples, the “average terminal hydrolyzable silyl group number” is “hydrolyzable silyl group introduced per molecule of polymer”, and from the number average molecular weight determined by ¹ H-NMR analysis and GPC. Calculated.

  NMR was measured at 23 ° C. using Bruker ASX-400 and deuterated chloroform as a solvent.

Production Example 1
Table 1 shows the amount of each raw material used.
(1) Polymerization step Acrylic acid ester (in the case of copolymerization, a predetermined amount of acrylic acid ester mixed beforehand) was deoxygenated. The inside of the stainless steel reaction vessel equipped with a stirrer was deoxygenated, and cuprous bromide and a part of the total acrylic ester (described as the initial charge monomer in Table 1) were charged and stirred with heating. Acetonitrile (described as “Acetonitrile for polymerization” in Table 1) and diethyl 2,5-dibromoadipate as an initiator were added and mixed. At the stage where the temperature of the mixture was adjusted to about 80 ° C., pentamethyldiethylenetriamine (hereinafter abbreviated as triamine). ) Was added to initiate the polymerization reaction. The remaining acrylic ester (described as an additional monomer in Table 1) was sequentially added to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during the polymerization is shown in Table 1 as a triamine for polymerization. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C. When the monomer conversion rate (polymerization reaction rate) was about 95% or more, volatile components were removed by devolatilization under reduced pressure to obtain a polymer concentrate.
(2) Diene reaction step 1,7-octadiene (hereinafter abbreviated as diene or octadiene) and acetonitrile (described in Table 1 as acetonitrile for diene reaction) are added to the concentrate, and a triamine (in Table 1, triamine for diene reaction) Added). While adjusting the internal temperature to about 80 ° C. to about 90 ° C., the mixture was heated and stirred for several hours to react the octadiene with the polymer terminal. Acetonitrile and unreacted octadiene were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer having an alkenyl group at the terminal.
(3) Rough purification step The concentrate is diluted with toluene, a filter aid, an adsorbent (KYOWARD 700SEN: manufactured by Kyowa Chemical), hydrotalcite (KYOWARD 500SH: manufactured by Kyowa Chemical)) are added, and 80 to After stirring at about 100 ° C., the solid component was filtered off. The filtrate was concentrated to obtain a crude polymer product.
(4) High-temperature heat treatment / adsorption purification step Crude polymer product, heat stabilizer (Sumilyzer GS: manufactured by Sumitomo Chemical Co., Ltd.), adsorbent (KYOWARD 700SEN, KYOWARD 500SH) are added, and devolatilization under reduced pressure. The temperature was raised while heating and stirring, and heating and stirring and vacuum devolatilization were performed for about several hours at a high temperature of about 170 ° C to about 200 ° C. Adsorbents (Kyoward 700SEN, Kyoward 500SH) were added, about 10 parts by weight of toluene was added to the polymer, and the mixture was further heated and stirred at a high temperature of about 170 ° C. to about 200 ° C. for several hours.

The treatment liquid was further diluted with toluene, and the adsorbent was filtered off. The filtrate was concentrated to obtain a polymer having alkenyl groups at both ends.
(5) Silylation step Polymer obtained by the above method, methyldimethoxysilane (DMS), methyl orthoformate (MOF), platinum catalyst [bis (1,3-divinyl-1,1,3,3-tetramethyl A predetermined amount of (disiloxane) platinum complex catalyst in isopropanol solution: hereinafter referred to as platinum catalyst] was mixed and heated to about 100 ° C. with stirring. After heating and stirring for about 1 hour, volatile components such as unreacted DMS were distilled off under reduced pressure to obtain a polymer “P1” having methoxysilyl groups at both ends. The number of silyl groups introduced per molecule of the obtained polymer, the molecular weight, and the molecular weight distribution are shown together in Table 1.

(Comparative synthesis example)
Table 2 shows the amount of each raw material used.
(1) Polymerization process The acrylic ester (premixed acrylic ester) was deoxygenated. The inside of the stainless steel reaction vessel equipped with a stirrer was deoxygenated, and cuprous bromide and a part of the total acrylic ester (described as the initial charge monomer in Table 1) were charged and stirred with heating. Acetonitrile (denoted as acetonitrile for polymerization in Table 1), diethyl 2,5-dibromoadipate (DBAE) as an initiator were added and mixed, and pentamethyldiethylenetriamine (hereinafter, referred to as “the temperature of the mixture” was adjusted to about 80 ° C.). (Abbreviated as triamine) was added to initiate the polymerization reaction. The remaining acrylic ester (described as an additional monomer in Table 1) was added sequentially to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during the polymerization is shown in Table 1 as a triamine for polymerization. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C.
(2) Oxygen treatment step When the monomer conversion rate (polymerization reaction rate) was about 95% or more, an oxygen-nitrogen mixed gas was introduced into the gas phase part of the reaction vessel. While maintaining the internal temperature at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction solution into contact with oxygen. Acetonitrile and unreacted monomer were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer. The concentrate was markedly colored.
(3) First crude purification Toluene was used as a diluent solvent for the polymer. The concentrate of (2) was diluted with about 100 to 150 kg of toluene with respect to 100 kg of the polymer, and a filter aid and an adsorbent (Kyoward 700 SEN, Kyoward 500 SH) were added. After introducing an oxygen-nitrogen mixed gas into the gas phase part of the reaction vessel, the mixture was heated and stirred at about 80 ° C. for several hours. Insoluble catalyst components were removed by filtration. The filtrate was colored and slightly turbid due to the polymerization catalyst residue.
(4) Second crude purification The filtrate was charged into a stainless steel reaction vessel equipped with a stirrer, and adsorbents (Kyoward 700SEN, Kyoward 500SH) were added. After introducing an oxygen-nitrogen mixed gas into the gas phase and heating and stirring at about 100 ° C. for several hours, insoluble components such as an adsorbent were removed by filtration. The filtrate was almost clear and clear. The filtrate was concentrated to obtain an almost colorless and transparent polymer.
(5) (Meth) acryloyl group introduction step The polymer is dissolved in about 100 parts by weight of N, N-dimethylacetamide (DMAC) with respect to the polymer in about 100 parts by weight, and potassium acrylate (about 2 with respect to the terminal Br group). Molar equivalent), heat stabilizer (H-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl), adsorbent (Kyoward 700SEN), and added at about 70 ° C. Stir for hours. DMAC was distilled off under reduced pressure, the polymer concentrate was diluted with about 100 kg of toluene with respect to 100 kg of the polymer, a filter aid was added, the solid content was filtered off, the filtrate was concentrated, and an acryloyl group was added to the end. A polymer [P2] having was obtained. Table 2 shows the number of acryloyl groups introduced per molecule of the obtained polymer, the number average molecular weight, and the molecular weight distribution.

Example 1
As a vinyl polymer (I) having a crosslinkable silyl group at the terminal, 100 parts of “P1” obtained in Synthesis Example 1 were combined with optomer SP-172 (photoacid generator, tri (alkylphenyl) sulfonium hexafluoroantimony). 1 part of the product, manufactured by Asahi Denka Kogyo Co., Ltd., 1 part of Irganox 1010 [pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals) The mixture was thoroughly mixed to obtain a curable composition.
Next, the obtained curable composition was irradiated with a high-pressure mercury lamp (184 W / cm, irradiation distance 5.4 cm, integrated light quantity 3030 mJ / cm ² ) to obtain a sheet-like cured product having a thickness of about 2 mm.
Moreover, the antifreeze liquid obtained by punching out the (1/3) mini dumbbell specified in JIS K 6251 from the obtained cured product and diluting with water to a weight fraction of 50% (Product name: Super Long Life Coolant Coolant, manufactured by Toyota Motor Corporation) Was kept at 130 ° C. and immersed for 170 hours. Tensile properties of the dumbbells before and after immersion were measured by the method defined in JIS K 6251.
Furthermore, the weight and volume swelling ratio of the sample were measured.

(Comparative Example 1)
[P2] To 100 parts, Darocur 1173 (photo radical polymerization initiator, manufactured by Ciba Specialty Chemicals) 0.2 part, Irgacure 819 (photo radical polymerization initiator, manufactured by Ciba Specialty Chemicals) 0.1 part Irganox 1010 [pentaerythritol tetrakis [ 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals Inc.] was added and mixed well to obtain a curable composition.
Irradiation was performed with a high-pressure mercury lamp (184 W / cm, irradiation distance 5.4 cm, integrated light quantity 3030 mJ / cm ² ), and a sheet-like cured product having a thickness of about 2 mm was obtained.
After producing a test sample in the same manner as in Example 1, the immersion test, the tensile property measurement, and the swelling rate were measured in the same manner as in Example 1.

上記実施例１では、比較例１での硬化物と比較して、引張り特性変化率、膨潤度が低く良好な耐不凍液性を示した。結果を表３に示す。 <Mechanical properties>
From the sheet-like curable compositions obtained in the above Examples and Comparative Examples, a (1/3) No. dumbbell test piece was punched out, and a tensile test was performed according to JIS K 6251 using an autograph made by Shimadzu. (Measurement conditions: 23 ° C. × 55% RH, pulling speed 200 mm / min). In Tables 1 to 3, M50 represents 50% modulus (strength at 50% elongation), M100 represents 100% modulus (strength at 100% elongation), and Tb represents strength at break, Eb indicates elongation at break.

In the said Example 1, compared with the hardened | cured material in the comparative example 1, the tensile property change rate and the swelling degree were low, and favorable antifreeze liquid resistance was shown. The results are shown in Table 3.

Claims (36)

A curable composition comprising a vinyl polymer (I) having an average of at least one crosslinkable silyl group and a compound (II) that generates an acid or a base upon irradiation with light,
The cured product after curing is characterized by having expansion resistance in a JIS K 6258 immersion test using a non-mineral brake fluid for automobiles defined in JIS K 2233 and an antifreeze fluid defined in JIS K 2234. A curable composition.   2. The curable composition according to claim 1, wherein, in the immersion test of JIS K 6258, the cured product after curing has an expansion resistance with a mass and volume change rate of 50% or less before and after liquid immersion. The curable composition according to claim 1 or 2, wherein the crosslinkable silyl group is represented by the general formula (1):
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO. (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. A plurality of R ′ may be the same or different.) ); When two or more of R ¹ or 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 of Y are present, They may be the same or different; a represents 0, 1, 2 or 3; b represents 0, 1, or 2; m represents an integer from 0 to 19, provided that a + mb Satisfy that ≧ 1.)   The curable composition according to any one of claims 1 to 3, wherein the vinyl polymer (I) has a molecular weight distribution of less than 1.8.   The curable composition according to any one of claims 1 to 4, wherein the main chain of the vinyl polymer (I) is a (meth) acrylic polymer.   The curable composition according to claim 5, wherein the (meth) acrylic polymer is an acrylic polymer.   The curable composition according to claim 6, wherein the acrylic polymer is an acrylic ester polymer.   The curable composition according to any one of claims 1 to 7, wherein the main chain of the vinyl polymer (I) is produced by a living radical polymerization method.   The curable composition according to claim 8, wherein the main chain of the vinyl polymer (I) is produced by an atom transfer radical polymerization method.   The curable composition according to any one of claims 1 to 9, wherein the vinyl polymer (I) has a number average molecular weight of 3000 or more.   The curable composition according to any one of claims 1 to 4, wherein the main chain of the vinyl polymer (I) is a polyisobutylene polymer.   The main chain structure between the crosslinkable silyl group at one end of the vinyl polymer (I) and the crosslinkable silyl group at a position different from the one end is composed of only a carbon-carbon bond. The curable composition according to any one of claims 1 to 11, wherein the curable composition comprises only a carbon-carbon bond and a carbon-silicon bond.   2. The compound (II) that generates an acid or a base upon irradiation with light is a compound that generates an acid selected from the group consisting of sulfonate esters, onium salts, and carboxylic acid esters. The curable composition in any one of from 12.   Compound (II) that generates an acid or a base by light irradiation is a compound that generates a base selected from the group consisting of carbamates, amides, oxime esters, α-cobalt complexes, and imidazoles. The curable composition according to any one of claims 1 to 12, which is characterized by the following.   Furthermore, an epoxy compound and / or an oxetane compound (III) are contained, The curable composition in any one of Claim 1-14 characterized by the above-mentioned.   The curable composition according to claim 15, wherein the epoxy compound and / or the oxetane compound (III) does not have an aromatic ring.   The curable composition according to claim 15 or 16, wherein the epoxy compound and / or oxetane compound (III) has a crosslinkable silyl group in the molecule.   Furthermore, the compound which has a carbon-carbon double bond which has radical polymerizability is contained, The curable composition in any one of Claim 1-17 characterized by the above-mentioned.   The curable composition according to any one of claims 1 to 18, further comprising a vinyl polymer (IV) having an average of at least one crosslinkable acryloyl group at its terminal. The curable composition according to claim 19, wherein the crosslinkable acryloyl group is represented by the general formula (2).
—OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)   The curable composition according to claim 19 or 20, wherein the vinyl polymer (IV) has a molecular weight distribution of less than 1.8.   The curable composition according to any one of claims 19 to 21, wherein the main chain of the vinyl polymer (IV) is a (meth) acrylic polymer.   The curable composition according to claim 22, wherein the (meth) acrylic polymer is an acrylic polymer. The curable composition according to claim 23, wherein the acrylic polymer is an acrylic ester polymer.   The curable composition according to any one of claims 19 to 24, wherein the main chain of the vinyl polymer (IV) is produced by a living radical polymerization method.   26. The curable composition according to claim 25, wherein the main chain of the vinyl polymer (IV) is produced by an atom transfer radical polymerization method.   The curable composition according to any one of claims 19 to 26, wherein the vinyl polymer (IV) has a number average molecular weight of 3000 or more.   The curable composition according to any one of claims 1 to 27, further comprising a trialkoxysilane compound or a tetraalkoxysilane compound having a molecular weight of 1000 or less.   The curable composition according to any one of claims 1 to 28, further comprising a tin-based compound.   A composition for in-situ molded gasket using the curable composition according to any one of claims 1 to 29.   A composition for sealing material, comprising the curable composition according to any one of claims 1 to 29.   A pressure-sensitive adhesive or adhesive composition comprising the curable composition according to any one of claims 1 to 29.   A composition for a potting agent comprising the curable composition according to any one of claims 1 to 29.   A composition for a coating agent comprising the curable composition according to any one of claims 1 to 29.   Hardened | cured material obtained by irradiating an active energy ray to the composition in any one of Claim 1-3.   36. In the immersion test of JIS K 6258, the mass and volume before and after immersion and the rate of change in strength and elongation at break of the tensile properties of JIS K 6251 are all 50% or less. Cured product.