JP5230907B2 - Primer composition - Google Patents

Description

The present invention relates to a primer composition containing a vinyl polymer having at least one crosslinkable silyl group, a silane coupling agent and a silanol condensation catalyst, and more particularly to a primer composition useful for a sealing material for construction.

In recent years, elastic sealing materials have been widely used in buildings, motor vehicles and the like. The sealing material is a material used for the purpose of filling the joints and gaps between various members to provide watertightness and airtightness. Accordingly, various base materials constituting the joints, the window frame and the like, that is, inorganic materials such as glass, ceramics, metal, cement, and mortar, and organic materials such as plastic (hereinafter, these are collectively referred to as “base material”). ) Must exhibit good adhesion. However, the adhesiveness of the sealing material itself is still insufficient, and the use of a primer is essential in many cases. As a sealing material to be applied to the joint portion of the interior and exterior of the general architecture, silicone, metamorphic silicone, polysulfide, and polyurethane and the like are well known. These sealing materials are selected based on the concept of “appropriate material for the right place” by selecting the appropriate sealing material for each type of joint (including the type of base material), and a dedicated primer suitable for each sealing material. Has been developed. Although it is not originally desirable to transfer different types of sealing materials to the above-mentioned various sealing materials, it may be unavoidable that different types of sealing materials may be transferred in the selection of a sealing material based on the concept of the right material or in factory construction. . Further, when repairing a sealing joint, after removing an existing sealing material, that is, a pre-sealed sealing material (referred to as a “base material” including the pre-sealed sealing material in the present invention), a new sealing material ( However, since the pre-sealing sealant cannot be completely removed, it is unavoidable that jointing of different kinds of sealant occurs. At this time, when the advance sealing material is a silicone sealing material, there is a problem that the sealing material other than the silicone sealing material cannot be used.
On the other hand, a sealing material containing a vinyl polymer having at least one crosslinkable silyl group and / or a polyether polymer having at least one crosslinkable silyl group as a main component (particularly a vinyl polymer is mainly used). Recently, an acrylic sealing material having a chain skeleton has been developed (see Patent Documents 1 and 2). This acrylic sealant is excellent in dynamic followability, heat resistance, weather resistance, water resistance, paintability, and has the characteristics of not contaminating the joint area, and has the performance as a universal sealant. No primer for acrylic sealant has been developed.

It is an object of the present invention to provide a primer composition for satisfactorily bonding a sealing material mainly composed of a vinyl polymer having at least one crosslinkable silyl group and various substrates, and particularly a silicone sealing. An object of the present invention is to provide a primer composition having good adhesiveness when a sealing material (post-striking) containing a vinyl polymer as a main component is succeeded to the material (pre-striking).

As a result of intensive studies in view of the above-described present situation, the present inventors have used a primer composition containing a vinyl polymer having at least one crosslinkable silyl group, a silane coupling agent, and a silanol condensation catalyst. The present inventors have found that the above problems can be improved and have reached the present invention.

That is, this invention relates to the primer composition formed by containing the following component.
(A) A vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1) (hereinafter sometimes referred to simply as “(A) vinyl polymer”)
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein R ¹ and R ² are the same or different and are each 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. A triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). When two or more 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 Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. },
(B) a silane coupling agent, and
(C) Silanol condensation catalyst.

The primer composition may further contain (D) a silicone resin.
The primer composition further comprises (E) a polyether polymer having at least one crosslinkable silyl group represented by the general formula (1) (hereinafter simply referred to as “(E) polyether polymer”). May be included).
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein R ¹ and R ² are the same or different and are each 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. A triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). When two or more 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 Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
The (C) silanol condensation catalyst is preferably an organic tin compound and / or an organic titanate.

It is preferable that the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the (A) vinyl polymer is less than 1.8.
The main chain of the (A) vinyl polymer is preferably a (meth) acrylic polymer.
The main chain of the vinyl polymer (A) is preferably produced by a living radical polymerization method, and more preferably produced by an atom transfer radial polymerization method.
The (A) vinyl polymer preferably has at least one crosslinkable silyl group represented by the general formula (1) at the molecular chain terminal.

The above-mentioned (A) vinyl polymer has the following steps:
(1) An organic halide or a sulfonyl halide compound is used as an initiator, and a vinyl monomer is radically polymerized using a transition metal complex as a catalyst to produce a vinyl polymer having a halogen at its terminal,
(2) A vinyl polymer having an alkenyl group at the terminal is produced by reacting an oxyanion having an alkenyl group to replace halogen.
(3) reacting a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1);
It is preferable that it is a polymer obtained by this.

The main chain of the polyether polymer (E) is preferably essentially polypropylene oxide.
The (B) silane coupling agent is preferably an amino group-containing silane coupling agent.
The primer composition of the present invention is preferably used for joining to the surface of the silicone sealant.

Below, the primer composition of this invention is explained in full detail.
The primer composition of the present invention is a composition comprising the following components.
(A) Vinyl polymer having at least one crosslinkable silyl group represented by the 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 the same or different and are each 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. A triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). When two or more 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 Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. },
(B) a silane coupling agent, and
(C) Silanol condensation catalyst.

<(A) Vinyl-based polymer>
The vinyl polymer having at least one crosslinkable silyl group represented by the following general formula (1) as a component (A) in one molecule of the polymer is crosslinked by forming a siloxane bond. .
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein R ¹ and R ² are the same or different and are each 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. A triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). When two or more 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 Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }

The alkyl group having 1 to 20 carbon atoms of R ¹ and R ² is not particularly limited, and for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl, tetradecyl , Octadecyl and the like.
It does not specifically limit as a C6-C20 aryl group of R < ¹ >, R < ² >, For example, a phenyl group, a naphthyl group, a toluyl group etc. are mentioned.
The aralkyl group having 7 to 20 carbon atoms of R ¹ and R ² is not particularly limited, and examples thereof include a benzyl group and a phenylethyl group.
The monovalent hydrocarbon group having 1 to 20 carbon atoms of R ′ is not particularly limited, and an alkyl group having 1 to 20 carbon atoms and the like are preferable, and specific examples thereof are the same as those described above.

The hydrolyzable group for Y is not particularly limited, and examples thereof include a hydrogen atom, a halogen 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. be able to. Among these, an alkoxy group is preferable from the viewpoint that the hydrolyzability is mild and easy to handle.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As an alkoxy group, a C1-C20 thing is preferable, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned.
As the acyloxy group, those having 1 to 20 carbon atoms are preferable, and examples thereof include formyloxy group, acetyloxy group, propionyloxy group and the like.
Preferred examples of the ketoximate group include those having 1 to 20 carbon atoms.
As the alkenyloxy group, those having 2 to 20 carbon atoms are preferable, and examples thereof include a vinyloxy group, an allyloxy group, and a butenyloxy group.

Y can be bonded to one silicon atom in the range of 1 to 3. A, b and m satisfy a + mb ≧ 1, that is, at least one Y is contained in the general formula (1). Further, the total sum of Y is preferably in the range of 1 to 5.
One silicon atom constituting the crosslinkable silyl group may be present, or two or more silicon atoms may be present. In the case of silicon atoms connected by a siloxane bond, up to about 20 may be used, and m is 0 to 19.

The monomer constituting the main chain of the vinyl polymer having at least one crosslinkable silyl group is not particularly limited as long as it is a vinyl monomer, and examples thereof include (meth) acrylic acid, methyl (meth) acrylate, Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, (meta ) N-pentyl acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid Phenyl, (meth) acrylic acid toluyl, (meth) acrylic acid benzyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 3-methoxypropyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic 2-hydroxypropyl acid, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid , Trifluoromethyl methyl (meth) acrylate, 2-trifluoromethyl ethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluoro (meth) acrylate Butylethyl, (meth) acrylic acid 2-perfluoro Ethyl, perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl (meth) acrylate, 2-perfluorohexyl (meth) acrylate (Meth) acrylic monomers such as ethyl, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate; styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrene Styrene monomers such as sulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, Maleic acid, ma Monoalkyl and dialkyl esters of inacid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenyl Maleimide monomers such as maleimide and cyclohexylmaleimide; Vinyl monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; Vinyl monomers containing amide groups such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, benzoic acid Vinyl esters such as vinyl and vinyl cinnamate; Alkenes such as ethylene and propylene; Conjugated dienes such as butadiene and isoprene Vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like.
These may be used alone or in combination of two or more.

In the above expression format, for example, (meth) acrylic acid indicates acrylic acid and / or methacrylic acid. The same applies to the following.
From the viewpoint of physical properties, the vinyl polymer having at least one crosslinkable silyl group is a (meth) acrylic compound obtained by synthesizing 40 wt% or more of a (meth) acrylic acid monomer among the above monomers. A polymer is preferred.
Furthermore, an acrylic polymer obtained by synthesizing using 30% by weight or more of an acrylic acid monomer among the above monomers is more preferable.

The number average molecular weight of the vinyl polymer having at least one crosslinkable silyl group is not particularly limited, but is preferably in the range of 500 to 100,000. If the number average molecular weight is less than 500, the original characteristics of the vinyl polymer tend to be hardly expressed, and if it exceeds 100,000, handling tends to be difficult.

The molecular weight distribution of the vinyl polymer having at least one crosslinkable silyl group, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is not particularly limited. However, it is preferable that the molecular weight distribution is narrow in order to keep the viscosity at the time of preparing the primer composition low to facilitate handling and to obtain sufficient cured product properties. The molecular weight distribution is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, still more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1. 3 or less.
The molecular weight distribution is most commonly measured by gel permeation chromatography (GPC). Chloroform or tetrahydrofuran (THF) is used as the mobile phase, a polystyrene gel column is used as the column, and the number average molecular weight and the like can be determined by a value in terms of polystyrene.

The method for synthesizing the vinyl polymer having at least one crosslinkable silyl group is not particularly limited, and various methods can be used. However, from the viewpoint of the versatility of the monomer and ease of control, a method of directly introducing a crosslinkable silyl group into the main chain by radical polymerization, and a specification that can be converted to a crosslinkable silyl group by a one-step or several-step reaction A method of converting this specific functional group into a crosslinkable silyl group after obtaining a vinyl polymer having a functional group of 1 by radical polymerization is preferred.

The radical polymerization method used in the method of synthesizing a vinyl polymer having a specific functional group containing a crosslinkable silyl group has a specific functional group using an azo compound, a peroxide, or the like as a polymerization initiator. Classifying into “general radical polymerization method” in which monomers and vinyl monomers are simply copolymerized and “controlled radical polymerization method” in which specific functional groups can be introduced at controlled positions such as terminals. Can do.

The “general radical polymerization method” is a simple method and can be used in the present invention, but a monomer having a specific functional group is introduced into the polymer only stochastically. For this reason, when trying to obtain a polymer having a high functionalization rate, it is necessary to use a large amount of this monomer, and there is a problem that the control range of physical properties is narrowed. Conversely, if the amount of the monomer having the specific functional group is small, there is a problem that the proportion of the polymer into which the specific functional group is not introduced increases. 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” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, and a polymerization growth terminal. 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 a termination reaction or the like.

The “chain transfer agent method” can obtain a polymer having a higher functionalization rate than the “general radical polymerization method” and can be used in the present invention. A chain transfer agent having a large amount of a specific functional group is necessary, and there is a problem in terms of economy including treatment. Further, like the above-mentioned “general radical polymerization method”, there is a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained because of free radical polymerization.

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 the 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, but in general, the terminal is inactivated and the terminal is activated. Pseudo-living polymerization in which is grown while in equilibrium. The definition in the present invention is also the latter.

The “living radical polymerization method” is not particularly limited as long as it is a radical polymerization method that satisfies the above definition. This “living radical polymerization method” has been actively studied in various groups in recent years, and examples thereof include, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994. One using a cobalt porphyrin complex as shown in Vol. 116, page 7943, or using a radical scavenger such as a nitroxide compound as shown in Macromolecules, 1994, Vol. 27, 7228 And “Atom Transfer Radical Polymerization (ATRP)” using an organic halide as an initiator and a transition metal complex as a catalyst.

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, or Sawamoto et al., Macromolecules 1995, 28, 1721. The method described in page etc. is mentioned.

Examples of the initiator used in the “atom transfer radical polymerization method” include organic halides, particularly organic halides having a highly reactive carbon-halogen bond, and sulfonyl halide compounds. Examples of the organic halide having a particularly highly reactive carbon-halogen bond include a carbonyl compound having a halogen at the α-position and a compound having a halogen at the benzyl-position. For example, initiators described in JP-A-11-130931, JP-A-11-158449 and the like can be used. These may be used alone or in combination of two or more.

The transition metal complex used as a catalyst for the above “atom transfer radical polymerization method” is not particularly limited. For example, a complex having a group 7 element, 8 group, 9 group, 10 group, or 11 element of the periodic table as a central metal, etc. Can be mentioned. Preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Among these, a copper complex is more preferable. These may be used alone or in combination of two or more.

The monovalent copper compound is not particularly limited. For example, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. Can be mentioned. 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 polyamine can be added.

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 can be 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 reaction can be performed without solvent or in various solvents. The solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; acetone, methyl ethyl ketone, and methyl isobutyl. Ketone solvents such as ketones; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; ethyl acetate, butyl acetate, etc. And ester solvents such as carbonate solvents such as ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more.
The above “atom transfer radical polymerization method” can be carried out in the range of 0 to 200 ° C. Preferably, it is the range of room temperature-150 degreeC.

Next, in the method for producing a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1), the method for introducing the crosslinkable silyl group is not particularly limited. For example, the following [A ] To [E] are preferably used, and these will be described in detail.
[A] A method of adding a hydrosilane compound having a crosslinkable silyl group to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst.
[B] A method of reacting a vinyl polymer having at least one hydroxyl group with a compound having a functional group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group.
[C] A method of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group together with a predetermined vinyl monomer when a vinyl polymer is synthesized by radical polymerization.
[D] A method of radical polymerization of a vinyl monomer using a chain transfer agent having a crosslinkable silyl group.
[E] A method of reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a stable carbanion having a crosslinkable silyl group.

The method for synthesizing the vinyl polymer having at least one alkenyl group used in the synthesis method [A] is not particularly limited, and examples thereof include the methods [Aa] to [Aj] described below. Can be mentioned.

[Aa] When synthesizing a vinyl polymer by radical polymerization, it has a polymerizable alkenyl group represented by the following general formula (2) and the like and a low polymerizable alkenyl group together with a predetermined vinyl monomer. A method in which a compound is also reacted.
_{^{H 2 C = C (R 3}} ) -R 4 -R 5 -C (R 6) = CH 2 (2)
(In the formula, R ³ represents hydrogen or a methyl group. R ⁴ represents —C (O) O—, or o-, m-, or p-phenylene group. R ⁵ represents a direct bond, or one or more groups. represents a divalent organic group having 1 to 20 carbon atoms that may have an ether bond .R ⁶ is hydrogen, an alkyl group having 1 to 10 carbon atoms, 7 to an aryl group or a carbon number of 6 to 10 carbon atoms 10 represents an aralkyl group.)
The time when the compound having both the polymerizable alkenyl group and the low polymerizable alkenyl group is reacted is not particularly limited, but when the obtained crosslinked product is expected to have rubber-like properties, living radical polymerization, It is preferable to react as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined vinyl monomer.

[Ab] When synthesizing a vinyl polymer by living radical polymerization, 1,5-hexadiene, 1,7-octadiene, 1,9-, at the end of the polymerization reaction or after completion of the reaction of the predetermined vinyl monomer. A method of reacting a compound having at least two alkenyl groups having low polymerizability such as decadiene.

In the following methods [Ac] to [Af], a vinyl polymer having at least one alkenyl group is obtained from a vinyl polymer having at least one carbon-halogen bond having high reactivity. Is the method. The polymer having at least one highly reactive carbon-halogen bond can be obtained by the methods [Ea] and [Eb] described later.

[Ac] A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with an alkenyl group-containing organometallic compound typified by organotin such as allyltributyltin or allyltrioctyltin. , A method of substituting the halogen with an alkenyl group-containing substituent.
[Ad] A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having an alkenyl group represented by the following general formula (3), etc. Substitution method.
^{M + C - (R 7)} (R 8) -R 9 -C (R 6) = CH 2 (3)
(Wherein, R ⁶ are the same as those described above .R ⁷ and R ⁸ are both carbanion C ^- an electron-withdrawing group, or one of the electron-withdrawing several other is hydrogen or a carbon in the group 1 to 10 for stabilizing R ⁹ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms which may contain one or more ether bonds, M ⁺ represents an alkali metal ion, or Indicates quaternary ammonium ion.)
As the electron withdrawing group for R ⁷ and R ⁸ , —CO ₂ R, —C (O) R and —CN are preferable. Here, R 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.

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

[Af] A vinyl polymer having at least one highly reactive carbon-halogen bond is represented by an alkenyl group-containing oxyanion represented by the following general formula (4) or the following general formula (5) or the like. The alkenyl group-containing carboxylate anion is reacted to replace the halogen with an alkenyl group-containing substituent.
_{^{H 2 C = C (R 6}} ) -R 10 -O - M + (4)
(In formula, R ^{< 6 >} and M ^<+> are the same as what was mentioned above. R ^{< 10} > shows a C1-C20 bivalent organic group which may contain the 1 or more ether bond.)
_{^{H 2 C = C (R 6}} ) -R 11 -C (O) O - M + (5)
(Wherein R ⁶ and M ⁺ are the same as those described above. R ¹¹ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds. .)

Furthermore, the vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, but the specific method is not particularly limited. For example, the following [A- g] to [A-j]. The vinyl polymer having at least one hydroxyl group can be obtained by the methods [Ba] to [Bi] described later.

[Ag] A method in which a base such as sodium hydroxide or sodium methoxide is allowed to act on a vinyl polymer having at least one hydroxyl group and then reacted with an alkenyl group-containing halide such as allyl chloride.
[Ah] A method of reacting a vinyl polymer having at least one hydroxyl group with an alkenyl group-containing isocyanate compound such as allyl isocyanate.
[Ai] A method of reacting a vinyl polymer having at least one hydroxyl group with an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine.
[Aj] A method in which a vinyl polymer having at least one hydroxyl group is reacted with an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst.

In the method for synthesizing a vinyl polymer having at least one alkenyl group, when a halogen atom is not directly involved in introducing the alkenyl group, such as the methods [Aa] and [Ab] described above, It is preferable to use a living radical polymerization method. In this case, the method [Ab] is more preferable because control is easier. Among the living radical polymerization methods, the atom transfer radical polymerization method is more preferable.

On the other hand, in the case of introducing an alkenyl group by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, such as the methods [Ac] to [Af] described above. At least one highly reactive carbon-halogen bond at the end obtained by radical polymerization (atom transfer radical polymerization method) using an organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst It is preferable to use a vinyl polymer having the same. From the viewpoint of easier control, the method [Af] is more preferable.

It does not specifically limit as a hydrosilane compound which has a crosslinkable silyl group used in the said synthesis method [A], For example, the compound etc. which are shown by following General formula (6) can be mentioned.
^{_{H- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (6)
(Wherein R ¹ , R ² , a, b, m and Y are the same as those described above.)
Among these, from the viewpoint of easy availability, a compound represented by the following general formula (7) is preferably used.
_{^{H-Si (R 2) 3}} -a (Y) a (7)
(Wherein R ² , Y and a are the same as described above.)

In the synthesis method [A], when the hydrosilane compound having the crosslinkable silyl group is added to the alkenyl group of the polymer, a transition metal catalyst is usually used as a hydrosilylation catalyst.
The transition metal catalyst is not particularly limited. For example, platinum alone; a platinum solid dispersed in a support such as alumina, silica, carbon black; chloroplatinic acid; chloroplatinic acid and alcohol, aldehyde, ketone, etc. complex; platinum - olefin complexes; platinum (0) - divinyltetramethyldisiloxane _{complex; RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2 , Compounds other than platinum compounds such as TiCl ₄ ; These may be used alone or in combination of two or more.

In the synthesis method [B], the method for synthesizing the vinyl polymer having at least one hydroxyl group, which is also used in the methods [Ag] to [Aj], is not particularly limited. [Ba] to [Bi] described in the above.

[Ba] When synthesizing a vinyl polymer by radical polymerization, a compound having both a polymerizable alkenyl group and a hydroxyl group represented by the following general formula (8) is also reacted with a predetermined vinyl monomer. How to make.
_{^{H 2 C = C (R 3}} ) -R 4 -R 5 -OH (8)
(Wherein R ³ , R ⁴ and R ⁵ are the same as described above.)
The timing of reacting the compound having both the polymerizable alkenyl group and the hydroxyl group is not particularly limited. However, when the obtained crosslinked product is expected to have rubber-like properties, it is a living radical polymerization, the end of the polymerization reaction or It is preferable to react as the second monomer after completion of the reaction of the predetermined vinyl monomer.

[Bb] When synthesizing a vinyl polymer 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 the above-mentioned vinyl monomer is radically polymerized using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide by a method as disclosed in JP-A-5-262808.
[Bd] A method in which the vinyl monomer is radically polymerized using hydrogen peroxide or a hydroxyl group-containing initiator by the methods disclosed in JP-A-6-239912, JP-A-8-283310, and the like.
[Be] A method in which a vinyl monomer is radically polymerized by using an excessive amount of alcohol by a method disclosed in JP-A-6-116312.

[Bf] The halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond is hydrolyzed or reacted with a hydroxyl group-containing compound by the method disclosed in JP-A-4-132706. To introduce a hydroxyl group into the terminal.
[Bg] A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group represented by the following general formula (9), etc. A method of substitution with a hydroxyl group-containing substituent.
^{M + C - (R 7)} (R 8) -R 9 -OH (9)
(Wherein R ⁷ , R ⁸ and R ⁹ are the same as described above.)
As the electron withdrawing group for R ⁷ and R ⁸ , —CO ₂ R, —C (O) R and —CN are preferable. Here, R is the same as described above.

[Bh] An enolic anion prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a metal alone or an organometallic compound such as zinc, an aldehyde or a ketone How to react.
[Bi] A vinyl polymer having at least one highly reactive carbon-halogen bond is represented by a hydroxyl group-containing oxyanion represented by the following general formula (10) or the like or the following general formula (11) or the like. A method of reacting a hydroxyl group-containing carboxylate anion to replace the halogen with a hydroxyl group-containing substituent.
^{HO-R 10 -O - M +} (10)
(Wherein R ¹⁰ and M ⁺ are the same as described above.)
^{HO-R 11 -C (O)} O - M + (11)
(Wherein R ¹¹ and M ⁺ are the same as described above.)

In the method for synthesizing a vinyl polymer having at least one hydroxyl group, when a halogen atom is not directly involved in introducing a hydroxyl group such as [Ba] to [Be], the living radical polymerization method is used. It is preferable to use it. In this case, the method [Bb] is more preferable because control is easier. Among the living radical polymerization methods, the atom transfer radical polymerization method is more preferable.

In addition, when the hydroxyl group is introduced by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, such as the methods [Bf] to [Bi] described above. Is obtained by radical polymerization (atom transfer radical polymerization method) using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, and has at least one highly reactive carbon-halogen bond at the terminal. It is preferable to use a vinyl polymer having the same. In this case, the method [Bi] is more preferable because control is easier.

The compound having a functional group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group used in the synthesis method [B] is not particularly limited. For example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanate. Examples thereof include propylmethyldimethoxysilane and γ-isocyanatopropyltriethoxysilane. These may be used alone or in combination of two or more.
Moreover, in the case of reaction in the said synthesis method [B], the catalyst of a well-known urethanation reaction can also be used if necessary.

The compound having both a polymerizable alkenyl group and a crosslinkable silyl group used in the synthesis method [C] is not particularly limited, and examples thereof include trimethoxysilylpropyl (meth) acrylate and methyldimethoxysilylpropyl (meth) acrylate. The compound etc. which are represented with the following general formula (12) can be mentioned.
_{^{H 2 C = C (R 3}} ) -R 4 -R 12 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) 3-a (Y) a (12)
(Wherein R ¹ , R ² , R ³ , R ⁴ , Y, a, b and m are the same as those described above. R ¹² contains a direct bond or one or more ether bonds. A divalent organic group having 1 to 20 carbon atoms.
These may be used alone or in combination of two or more.

In the synthesis method [C], the timing for reacting the compound having the polymerizable alkenyl group and the crosslinkable silyl group is not particularly limited. However, when the resulting crosslinked product is expected to have rubbery properties, a living radical is used. In the polymerization, it is preferable to react as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined vinyl monomer.

The chain transfer agent having a crosslinkable silyl group used in the synthesis method [D] is not particularly limited, and is disclosed in, for example, Japanese Patent Publication Nos. 3-14068 and 4-55444. , Mercaptans having a crosslinkable silyl group, hydrosilanes having a crosslinkable silyl group, and the like. Furthermore, in order to increase the introduction rate of the crosslinkable silyl group, a radical initiator having a crosslinkable silyl group may be used in combination.

In the synthesis method [E], at least a highly reactive carbon-halogen bond used also in the methods [Ac] to [Af] and [Bf] to [Bi] is used. The method for synthesizing one vinyl polymer is not particularly limited, and examples thereof include the following methods [Ea] and [Eb].
[Ea] Radical polymerization using a halide such as carbon tetrachloride, ethylene chloride, carbon tetrabromide or methylene bromide as a chain transfer agent by the method disclosed in JP-A-4-132706. Method to perform (chain transfer agent method).
[Eb] An atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst.

It does not specifically limit as a stable carbanion which has a crosslinkable silyl group used in the said synthesis method [E], The compound etc. which are represented by following General formula (13) can be mentioned.
^{M + C - (R 7)} (R 8) -R 13 -C (H) (R 14) -CH 2 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) _3-a (Y) _a (13)
(Wherein R ¹ , R ² , R ⁷ , R ⁸ , Y, a, b, m and M ⁺ are the same as those described above. R ¹³ represents a direct bond or one or more ether bonds. R ¹⁴ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl having 7 to 10 carbon atoms. Group.)
As the electron withdrawing group for R ⁷ and R ⁸ , —CO ₂ R, —C (O) R and —CN are preferable. Here, R is the same as described above.

When a foamed product obtained by foaming and curing the primer composition of the present invention is particularly required to have rubbery properties, the molecular weight between crosslinking points that greatly affects rubber elasticity can be increased. At least one is preferably at the end of the molecular chain. More preferably, it has all crosslinkable silyl groups at the molecular chain ends.
A method for producing a vinyl polymer having at least one crosslinkable silyl group at its molecular terminal, in particular, a (meth) acrylic polymer is disclosed in Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, No. 6-211922 and the like. 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 / The value of the molecular weight distribution represented by Mn is generally as large as 2 or more, and there is a problem that the viscosity becomes 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. It is preferable.

Therefore, the vinyl polymer having at least one hydroxyl group, halogen or alkenyl group used when synthesizing the vinyl polymer having at least one crosslinkable silyl group has these functional groups at the molecular chain ends. Those are preferred.
In order to obtain a vinyl polymer having at least one crosslinkable silyl group at the molecular chain terminal using the “atom transfer radical polymerization method” more preferable among the “living radical polymerization methods”, as an initiator, It is preferable to use an organic halide or a sulfonyl halide compound having two or more starting points. The vinyl polymer having at least one highly reactive carbon-halogen bond at the molecular chain end thus obtained is obtained by the above-described method, and the vinyl polymer having at least one crosslinkable silyl group at the molecular chain end. Can be easily changed.

It does not specifically limit as an organic halide which has 2 or more of the said starting points, or a halogenated sulfonyl compound, For example, the following compound can be mentioned.
Specific examples are:
_{o-, m-, p-XCH 2} -C 6 H 4 -CH 2 X, o-, m-, p-CH 3 C (H) (X) -C 6 H 4 -C (H) (X) _{CH 3, o-, m-, p-} (CH 3) 2 C (X) -C 6 H 4 -C (X) (CH 3) 2
(In the above formula, C ₆ H ₄ represents a phenylene group. X represents chlorine, bromine, or iodine.)
_{RO 2 C-C (H)} (X) - (CH 2) n -C (H) (X) -CO 2 R, RO 2 C-C (CH 3) (X) - (CH 2) n -C _{(CH 3) (X) -CO} 2 R, RC (O) -C (H) (X) - (CH 2) n -C (H) (X) -C (O) R, RC (O) - _{C (CH 3) (X)} - (CH 2) n -C (CH 3) (X) -C (O) R
(In the above formula, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group. N represents an integer of 0 to 20, and X represents chlorine, bromine, or iodine.)
_{XCH 2 -C (O) -CH 2} X, H 3 C-C (H) (X) -C (O) -C (H) (X) -CH 3, (H 3 C) 2 C (X) _{-C (O) -C (X)} (CH 3) 2, C 6 H 5 C (H) (X) - (CH 2) n -C (H) (X) C 6 H 5
(In the above formula, X represents chlorine, bromine or iodine, and n represents an integer of 0 to 20.)
_{XCH 2 CO 2 - (CH 2} ) n -OCOCH 2 X, CH 3 C (H) (X) CO 2 - (CH 2) n -OCOC (H) (X) CH 3, (CH 3) 2 C ( _{X) CO 2 - (CH 2} ) n -OCOC (X) (CH 3) 2
(In the above formula, X represents chlorine, bromine or iodine, and n represents an integer of 1 to 20.)
_{XCH 2 C (O) C (} O) CH 2 X, CH 3 C (H) (X) C (O) C (O) C (H) (X) CH 3, (CH 3) 2 C (X) _{C (O) C (O)} C (X) (CH 3) 2, o-, m-, p-XCH 2 CO 2 -C 6 H 4 -OCOCH 2 X, o-, m-, p-CH 3 _{C (H) (X) CO} 2 -C 6 H 4 -OCOC (H) (X) CH 3, o-, m-, p- (CH 3) 2 C (X) CO 2 -C 6 H 4 - OCOC (X) (CH ₃ ) ₂ , o-, m-, p-XSO ₂ —C ₆ H ₄ —SO ₂ X
(In the above formula, X represents chlorine, bromine or iodine.)
Etc. These may be used alone or in combination of two or more.

Further, in order to obtain a vinyl polymer having a crosslinkable silyl group at both molecular chain ends, an organic halide or sulfonyl halide compound having two starting points as an initiator in the above-mentioned “atom transfer radical polymerization method”, etc. In addition to the method using, a method using an organic halide having a crosslinkable silyl group is also preferred.

It does not specifically limit as said organic halide which has a crosslinkable silyl group, For example, the compound etc. which are represented by following General formula (14) or (15) can be mentioned.
^{R 15 R 16 C (X)} -R 17 -R 18 -C (H) (R 19) CH 2 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) 3- _a (Y) _a (14)
(In the formula, R ¹ , R ² , a, b, m, X and Y are the same as those described above. R ¹⁵ and R ¹⁶ are the same or different and are hydrogen or an alkyl group having 1 to 20 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, R ¹⁵ and R ¹⁶ may be connected to each other at the other end, and R ¹⁷ is —C (O) O—. , -C (O)-, or o-, m-, p-phenylene group R ¹⁸ is a direct bond or a divalent valence having 1 to 10 carbon atoms which may contain one or more ether bonds. R ¹⁹ 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.)
_{^{(R 2) 3-a (}} Y) a Si- [OSi (R 1) 2-b (Y) b] m -CH 2 -C (H) (R 19) -R 18 -C (R 15) ( X) -R ¹⁷ -R ¹⁶ (15)
(Wherein R ¹ , R ² , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , a, b, m, X and Y are the same as those described above.)

When the above-mentioned “atom transfer radical polymerization method” is performed using the organic halide having a crosslinkable silyl group as an initiator, a carbon-halogen having a crosslinkable silyl group at one end and a high reactivity at the other end. A vinyl polymer having a bond is obtained. A vinyl polymer having a crosslinkable silyl group at both molecular chain ends can be obtained by converting the terminal halogen atom of this vinyl polymer into a crosslinkable silyl group-containing substituent using the above-described method or the like. .
The crosslinkable silyl group can also be obtained by coupling halogen atoms of the vinyl polymer with a compound having two or more of the same or different functional groups that can replace the halogen atom at the terminal end. Can be obtained at both molecular chain terminals.
The compound having two or more of the same or different functional groups that can replace the halogen atom at the terminal end is not particularly limited. For example, polyol, polyamine, polycarboxylic acid, polythiol, salts thereof; alkali metal sulfide, etc. Can be mentioned.

Further, in the above “atom transfer radical polymerization method”, when an organic halide having an alkenyl group is used as an initiator, a vinyl polymer having an alkenyl group at one end and a halogen atom at the other end can be obtained. If the halogen atom at the terminal of this vinyl polymer is converted into an alkenyl-containing substituent using the above-described method, a vinyl polymer having an alkenyl group at both molecular chain terminals can be obtained. If these alkenyl groups are converted into a crosslinkable silyl group by the above-described method or the like, a vinyl polymer having the crosslinkable silyl group at both molecular chain ends can be obtained.

The vinyl polymer having at least one crosslinkable silyl group at the end of the molecular chain can be obtained by combining the above-described methods and the like as needed, but the following synthesis examples a and b are given as typical synthesis steps. it can.

Synthesis process a
(A-1) a step of synthesizing a vinyl polymer having a halogen atom at its terminal by radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst;
(A-2) The vinyl polymer having a halogen atom at the terminal obtained in the step (a-1) is reacted with an oxyanion having an alkenyl group to replace the halogen, whereby an alkenyl group is formed at the terminal. A step of synthesizing a vinyl polymer having, and
(A-3) A hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) is added to the terminal alkenyl group of the vinyl polymer having an alkenyl group at the terminal obtained in the step (a-2). And a synthesis step comprising a step of converting to a substituent containing a crosslinkable silyl group.

Synthesis step b
(B-1) a step of synthesizing a vinyl polymer by polymerizing a vinyl monomer by a living radical polymerization method,
(B-2) A vinyl polymer having an alkenyl group at the terminal by reacting the vinyl polymer obtained in the step (b-1) with a compound having at least two alkenyl groups having low polymerizability. Synthesizing, and
(B-3) A hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) on the terminal alkenyl group of the vinyl polymer having an alkenyl group at the terminal obtained in the step (b-2). A synthesis step comprising a step of adding and converting to a substituent containing a crosslinkable silyl group.

<(B) Silane coupling agent>
The primer composition of the present invention contains (B) a silane coupling agent. The silane coupling agent forms a tough film by reaction with a vinyl polymer having at least one crosslinkable silyl group as the component (A), and various substrates (glass, ceramics, metal, cement, Inorganic materials such as mortar, organic materials such as plastic, and the like) and a sealing material mainly composed of a vinyl polymer having at least one crosslinkable silyl group are improved.

A silane coupling agent is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as a hydrolyzable silicon group) and other functional groups.
As an example of this hydrolysable silicon group, the group whose Y is a hydrolysable group can be mentioned among groups represented by the general formula (1). Specific examples of the hydrolyzable group include the groups already exemplified, and 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 preferably 3 or more.
Examples of functional groups other than hydrolyzable silicon groups include primary, secondary, tertiary amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, halogens and the like. Of these, primary, secondary, tertiary amino groups, mercapto groups, isocyanate groups, isocyanurates and the like are preferable, and amino groups are particularly preferable.

Specific examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl). ) Aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, Amino group-containing silanes such as γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane Γ-Merka Mercapto group-containing silanes such as topropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ- Epoxy such as glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Group-containing silanes; carbo such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane Xysilanes; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane; γ-chloropropyltrimethoxysilane Halogen-containing silanes such as tris (trimethoxysilyl) isocyanurate; isocyanurate silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanate Isocyanate group-containing silanes such as propylmethyldimethoxysilane. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, blocked isocyanate silanes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc., which are derivatives of these, are also used as silane coupling agents. Can be used.

The blending amount of the (B) component silane coupling agent is (A) a vinyl polymer or (E) a vinyl polymer and (E) when it further contains a polyether polymer. From the viewpoint of adhesiveness, 0.1 to 0.1 parts by weight of the total amount of the polyether polymer (hereinafter sometimes simply referred to as “total amount of polymer having at least one crosslinkable silyl group”). 500 parts by weight is preferable, and 0.5 to 100 parts by weight is more preferable.
The silane coupling agent may be used alone or in combination of two or more.
In addition, the primer composition of this invention can also use adhesiveness imparting agents other than a silane coupling agent.

<(C) Silanol condensation catalyst>
The primer composition of the present invention contains (C) a silanol condensation catalyst. The silanol condensation catalyst acts as a curing catalyst for (A) a vinyl polymer and (E) a polyether polymer. As a result, (A) the vinyl polymer, or (A) the vinyl polymer and (E) the polyether polymer form a strong film as a primer layer.
Examples of the silanol condensation catalyst include a tin-based catalyst, a titanium-based catalyst, a zirconium-based catalyst, and an aluminum-based catalyst, and organic titanate esters and / or organic tin compounds are preferable.

Examples of organic titanate esters include organic titanate esters, titanium chelate compounds, chelate compounds based on titanium silicate esters, titanate coupling agents, and partial hydrolysis condensates thereof.
Specific examples of the organic titanates include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetrakis (2-ethylhexyl) titanate, tetrastearyl titanate, tetramethyl titanate, diethoxybis (acetylacetonato) titanium, diisopropyl bis (Acetylacetonato) titanium, diisopropoxybis (ethylacetoacetate) titanium, isopropoxy (2-ethyl-1,3-hexanediolato) titanium, di (2-ethylhexoxy) bis (2-ethyl-1,3) -Hexanediolato) titanium, di-n-butoxybis (triethanolaminato) titanium, tetraacetylacetonate titanium, hydroxybis (lactato) titanium, and hydrolytic condensates thereof It is possible.
Moreover, as a specific example of a titanate coupling agent,

The compound shown by these, and these hydrolysis-condensation products can also be mentioned.
Of the above organic titanates, the general formula (16)
Ti (OR) ₄ (16)
(In the formula, R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R may be the same or different.)
A compound represented by the formula is more preferable because the effect of improving adhesiveness is particularly high.

Specific examples of organic tin compounds include tin carboxylates, dialkyltin oxides, and general formula (17)
_{Q d Sn (OZ) 4-} d, _{or, [Q 2 Sn (OZ)} ] 2 O (17)
(In the formula, Q is a monovalent hydrocarbon group having 1 to 20 carbon atoms, Z is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a functional group capable of forming a coordination bond to Sn inside itself. Represents an organic group having a functional group, d represents 0, 1, 2, or 3. In addition, when a plurality of Q and Z are present, they may be the same or different.
And the like.
In addition, it does not specifically limit as a C1-C20 monovalent hydrocarbon group of Q and Z, For example, the same thing etc. as the group illustrated by said R 'etc. are mentioned.
Although it does not specifically limit as an organic group which has a functional group which can form a coordinate bond with Sn inside self, For example, a carbonyl group, an amino group, etc. are mentioned.

Further, a tetravalent tin compound such as dialkyl tin oxide or dialkyl tin diacetate and a low molecular silicon compound having a hydrolyzable silicon group such as tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane or phenyltrimethoxysilane. The reactants are also effective as curing catalysts that significantly accelerate the silanol condensation reaction.
Among these, compounds represented by the general formula (17), that is, chelate compounds such as dibutyltin bisacetylacetonate and tin alcoholates have high activity as silanol condensation catalysts, and the film formation rate of the primer composition is high. This is more preferable.

Specific examples of the tin carboxylates include, for example, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, Dibutyltin diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctyl Malate etc. are mentioned.
Specific examples of the dialkyl tin oxides include dibutyl tin oxide, dioctyl tin oxide, a mixture of dibutyl tin oxide and phthalate ester, and the like.
Specific examples of the chelate compound include:

However, it is not limited to these. Of these, dibutyltin bisacetylacetonate is most preferred because of its high catalytic activity, low cost, and availability.
Specific examples of the tin alcoholates include:

However, it is not limited to these. Of these, dialkyltin dialkoxides are preferred. In particular, dibutyltin dimethoxide is more preferable because of its low cost and easy availability.

Moreover, you may use silanol condensation catalysts other than said titanate ester and / or an organotin compound. Specifically, inorganic tin compounds such as tin octylate; aluminum-based curing catalysts such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate; lead octylate Butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenyl Guanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methyl Amine-based curing catalysts such as morpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), or salts of these amine compounds with carboxylic acids; Low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, etc. Examples thereof include silanol condensation catalysts such as silane coupling agents having an amino group, and other known silanol condensation catalysts such as other acidic catalysts and basic catalysts.

The above silanol condensation catalysts may be used alone or in combination of two or more.
The blending amount of the (C) component silanol condensation catalyst is (A) a vinyl polymer, or (E) a polyether polymer when it further contains a (A) vinyl polymer and (E) poly. 1 to 1000 parts by weight is preferable with respect to 100 parts by weight of the total amount of the ether-based polymer (hereinafter sometimes simply referred to as “total amount of polymer having at least one crosslinkable silyl group”). Part by weight is more preferred. When the blending amount of the silanol condensation catalyst is less than 1 part by weight, the film formation rate may be slow, and it may be difficult to form a film sufficiently. On the other hand, when the compounding amount of the silanol condensation catalyst exceeds 1000 parts by weight, the open time is shortened and workability tends to be lowered.

<(D) Silicone resin>
The primer composition of the present invention can further contain a silicone resin as the component (D). The silicone resin improves wettability, improves the expression of adhesiveness, and improves the brushing suitability of the primer composition.

As the silicone resin, those generally used as the resin component of the silane primer can be used. For example, the average unit formula is
R ²⁰ _e SiO _{(4-ef) / 2} (OR ²¹ ) _f
(In the formula, R ²⁰ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ²¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, e is 0.8 to 1.8, and f is in one molecule. Represents the value where the number of hydroxyl groups or alkoxy groups bonded to the silicon atom is 1 or more.)
And an organopolysiloxane resin containing a silicon atom-bonded hydroxyl group or alkoxy group.
The monovalent hydrocarbon group having 1 to 6 carbon atoms of R ²⁰ is not particularly limited, and examples thereof include alkyl groups having 1 to 6 carbon atoms (methyl group, ethyl group, propyl group, etc.), 6 alkenyl groups (vinyl group, allyl group, etc.) and the like. The alkyl group having 1 to 6 carbon atoms R ^21, not particularly limited, R ¹ described ^above, those such as 1 to 6 carbon atoms of the exemplary alkyl groups R ² can be mentioned.

When the primer composition of the present invention contains the component (D) silicone resin, the blending amount thereof is (A) a vinyl polymer or (E) a polyether polymer ( With respect to 100 parts by weight of the total amount of A) vinyl polymer and (E) polyether polymer (hereinafter sometimes simply referred to as “total amount of polymer having at least one crosslinkable silyl group”), From an adhesive viewpoint, 5-1000 weight part is preferable and 5-200 weight part is more preferable.

<(E) polyether polymer>
The primer composition of the present invention may further contain a polyether polymer having at least one crosslinkable silyl group represented by the general formula (1) in one molecule of the polymer as the component (E). it can.
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein R ¹ and R ² are the same or different and are each 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. A triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). When two or more 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 Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }

The primer composition of the present invention has a low modulus and a high modulus by containing (E) a polyether polymer when (A) a sealing material mainly composed of a vinyl polymer (post-molding) is succeeded. A rubber-like cured product having an elongation can be realized, but a rubber-like cured product having a high modulus and a low elongation can also be provided depending on applications. That is, in the primer composition of the present invention, the amount and type of the (E) polyether polymer can be appropriately set according to the composition component of the post-sealing sealant to which the primer composition is applied.

(E) The main chain of the polyether polymer is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, polybutylene oxide, and polyphenylene oxide. Of these, the main chain of the (E) polyether polymer is preferably essentially polyoxyalkylene, more preferably essentially polypropylene oxide, which includes, in addition to propylene oxide, ethylene oxide, Butylene oxide, phenylene oxide and the like may be included. In addition, (E) the polyether polymer may or may not contain a urethane bond in the main chain.
Here, "the main chain is essentially polypropylene oxide" means that the propylene oxide unit occupies 50 mol% or more of the repeating units constituting the main chain, preferably 70 mol% or more, more preferably Is 90 mol% or more.
The lower the viscosity, the better the handleability, so that the molecular weight distribution (Mw / Mn) of the polypropylene oxide polymer is more preferably 1.5 or less.

(E) Although the crosslinkable silyl group in a component is shown by the above-mentioned general formula (1), each symbol etc. in a formula are the same as what was mentioned above. The crosslinkable silyl group in component (E) may have the same structure as the crosslinkable silyl group in component (A) or may have a different structure.
(E) The number of crosslinkable silyl groups possessed by the polyether polymer is at least one in one molecule of the polymer, but from the viewpoint of the curability of the composition, it may have more than one on average. More preferably, it is 1.1 to 4.0 on average, more preferably 1.5 to 2.5 on average.
Moreover, from the viewpoint of rubber elasticity of the cured product, the crosslinkable silyl group is preferably at the end of the polyether polymer, and more preferably at both ends of the polymer.

(E) The method for producing the polyether-based polymer is not particularly limited, and may be a conventionally known method, for example, described in JP-A-50-156599, JP-A-55-125121, and the like. Manufacturing methods and the like.
In terms of trade names, MS polymers S-203 and S-303 (manufactured by Kaneka Corporation) can be exemplified, but are not limited thereto.

In the case where the primer composition of the present invention contains the polyether polymer of component (E), the blending amount thereof is (A) the vinyl polymer and (E) the polyether polymer contained in the post-sealing sealant. It is preferable to match the mixing ratio of the coalescence, and the weight ratio ((A) / (E)) is preferably in the range of 99/1 to 1/99, and is preferably in the range of 95/5 to 5/95. More preferably, it is still more preferably in the range of 70/30 to 30/70. When the blend ratio of the (A) vinyl polymer is small, the excellent weather resistance of the primer composition may be difficult to be expressed.

<Primer composition>
The primer composition of the present invention is a composition comprising the components (A), (B) and (C) as described above. Moreover, (D), (E) component can be contained as needed.
Furthermore, the primer composition of the present invention may be blended with various additives and the like as necessary in order to adjust the physical properties.

In the primer composition of the present invention, a solvent can be used in order to adjust the composition to a viscosity suitable for primer application work. The solvent is not particularly limited as long as it dissolves the components (A) to (E) of the present invention.
Specific examples of such solvents include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and petroleum solvents; halogen solvents such as trichloroethylene; ester solvents such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, and methyl isobutyl. Examples include ketone solvents such as ketones; alcohol solvents such as methanol, ethanol, and isopropanol; silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. These solvents may be used alone or in combination of two or more.

When the solvent is used, the blending amount is (A) a vinyl polymer, or (E) a polyether polymer when it further contains a polyether polymer (A) a vinyl polymer and (E) a polyether system. 100 parts by weight of the total amount of polymer (hereinafter, sometimes simply referred to as “total amount of polymer having at least one crosslinkable silyl group”) (hereinafter, “parts by weight” may be simply referred to as “parts”) On the other hand, about 50 to 500000 parts are preferable, and 500 to 5000 parts are more preferable. From the viewpoint of lowering the viscosity of the primer composition and better workability, it is preferably 50 parts or more, and from the point of obtaining sufficient adhesion, it is preferably 500,000 parts or less.

Various anti-aging agents can be added to the primer composition of the present invention as required in order to improve adhesion durability. Such antioxidants include phenolic antioxidants, aromatic amine antioxidants, sulfur hydroperoxide decomposers, phosphorus hydroperoxide decomposers, benzotriazole ultraviolet absorbers, salicylate ultraviolet absorbers, and benzophenones. Examples include ultraviolet absorbers, hindered amine light stabilizers, nickel light stabilizers, and the like.

Specific examples of the phenolic antioxidant include 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,5 -Di-t-butylhydroquinone, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl -4-hydroxyphenyl) propionate], 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'- Examples thereof include thiobis (3-methyl-6-tert-butylphenol). Specific examples of the aromatic amine antioxidant include N, N'-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and the like. Specific examples of the sulfur hydroperoxide decomposer include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. Can be illustrated. Specific examples of the phosphorus hydroperoxide decomposer include diphenylisooctyl phosphite and triphenyl phosphite. Specific examples of the benzotriazole ultraviolet absorber include 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole and 2- (3-t-butyl-5-methyl). 2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole and the like. It can be illustrated. Specific examples of the salicylate ultraviolet absorber include 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5′-di-t-butyl-4′-hydroxybenzoate, and the like. it can. Specific examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxy. Examples include benzophenone and 2-hydroxy-4-benzyloxybenzophenone. Specific examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl). ) Sebacate, 1- {2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -4- [3- (3,5-di-tert-butyl-4) -Hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine and the like. Specific examples of the nickel-based light stabilizer include nickel dibutyldithiocarbamate, [2,2′-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel (II), [2,2′- Examples thereof include thiobis (4-t-octylphenolate)]-n-butylamine nickel (II).

These anti-aging agents may be used alone or in combination of two or more. It may function more effectively when used in combination than when used alone. In particular, a combination of a phenolic antioxidant, a salicylate ultraviolet absorber, and a hindered amine light stabilizer is more preferable because it significantly improves the weather resistance of the vinyl polymer as the component (A).

When using an anti-aging agent, the compounding quantity is preferably 1 to 1000 parts by weight and more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the component (A). When the blending amount is less than 1 part by weight, the effect of improving the weather resistance may not be sufficient, and when it exceeds 1000 parts by weight, the cost of the primer composition tends to increase or the adhesiveness tends to decrease.

Furthermore, the primer composition of the present invention includes a weather resistance improver (a compound having an unsaturated group that undergoes polymerization by reacting with oxygen in the air or light in order to further improve the weather resistance. A polymerizable substance) can be added as necessary. These are effective even if used alone or in combination.

The compound having an unsaturated group in the molecule that undergoes polymerization by reacting with oxygen in the air indicates an oxidative polymerization reactive substance. Specific examples of the oxidative polymerization reactive substance include ester compounds of unsaturated higher fatty acids and alcohols; diene polymers and copolymers such as 1,2-polybutadiene, 1,4-polybutadiene, and C5-C8 diene; And various modified products (maleinized modified products, boiled oil modified products, etc.) of the polymers and copolymers.

Specific examples of the above-mentioned unsaturated higher fatty acid ester compounds include unsaturated higher fatty acids such as oleic acid, linoleic acid, linolenic acid, eleostearic acid, licanoic acid, ricinoleic acid, arachidonic acid, punicic acid, canulpinic acid and the like. And monohydric alcohols such as methanol and ethanol, dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as trimethylolpropane and glycerin, tetrahydric alcohols such as pentaerythritol, hexahydric alcohols such as sorbid, silicon There is an ester compound obtained by a condensation reaction with an alcohol selected from an organic silicon compound having a hydroxyl group through an organic group bonded to an atom. Among these ester compounds, linseed oil, tung oil, soybean oil, asa seed oil, isano oil, urushi kernel oil, sesame oil, oil deer, mainly composed of triglycerin ester which is an ester of unsaturated higher fatty acid and glycerin. Oil, kayak oil, walnut oil, poppy oil, cherry seed oil, pomegranate seed oil, safflower oil, tobacco seed oil, tomato seed kernel oil, rubber seed oil, sunflower seed oil, grape kernel oil, spinach seed oil, honey seed oil Is more preferable because it is inexpensive and easily available. Among the above-mentioned drying oils, tung oil, prickly oil, pomegranate seed oil, spinach seed oil having triglycerin ester of a conjugated unsaturated higher fatty acid such as eleostearic acid, licanoic acid, punicic acid, canulpinic acid as a main component And the like are more preferable because they have a high effect of improving weather resistance.
The compound having in its molecule an unsaturated group that undergoes polymerization by reacting with oxygen in the air may be used alone or in combination of two or more.

That is, the photopolymerizable substance is a compound having an unsaturated group that causes a polymerization reaction when a double bond in a molecule is activated by irradiation with light.
Representative examples of the photopolymerizable unsaturated group contained in this photopolymerizable substance include vinyl group, allyl group, vinyl ether group, vinyl thioether group, vinylamino group, acetylenically unsaturated group, acryloyl group, methacryloyl group, Although a styryl group, a cinnamoyl group, etc. can be mentioned, Among these, an acryloyl group or a methacryloyl group is preferable because of high photoinitiation efficiency.

Examples of the photopolymerizable substance having a acryloyl group or a methacryloyl group as a photosensitive group include acrylamide derivatives, methacrylamide derivatives, (meth) acrylates, etc. Among these, (meth) acrylates are of a kind. It is more preferable because it is easily available. In the present specification, (meth) acrylate is a general term for acrylate and methacrylate.
Specific examples of the (meth) acrylate include propylene (or butylene, ethylene) glycol di (meth) acrylate having two functional groups, trimethylolpropane tri (meth) acrylate having three functional groups, pentaerythritol tri ( And (meth) acrylate, pentaerythritol tetra (meth) acrylate having 4 or more functional groups, dipentaerythritol penta, and hexa (meth) acrylate.
The (meth) acrylate oligomer is also a photopolymerizable substance. Specific examples of the oligomer include oligoesters having a molecular weight of 10,000 or less, such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate. Can be mentioned. The number of acrylic or methacrylic unsaturated groups in one molecule is preferably 2 or more, and more preferably 3 or more. The effect of improving the weather resistance of the unsaturated acrylic compound increases as the number of functional groups increases.
A photopolymerizable substance may be used alone or in combination of two or more.

When using a weather-resistant adhesive improvement agent, 1-1000 weight part is preferable with respect to 100 weight part of (A) component, and, as for the compounding quantity, 1-100 weight part is more preferable. When the blending amount is less than 1 part by weight, the effect of improving the weather resistance may not be sufficient, and when it exceeds 1000 parts by weight, the storage stability of the primer composition may be lowered.

Various fillers can be added to the primer composition of the present invention as needed for viscosity adjustment.
Specific examples of the filler include, for example, wood powder, parb, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, fume silica, precipitated silica, Examples thereof include anhydrous silicic acid, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder, and zinc dust. Of these fillers, precipitated silica, fume silica, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. These fillers may be used alone or in combination of two or more.
When using a filler, the compounding quantity is preferably 1 to 10000 parts by weight, more preferably 10 to 1000 parts by weight with respect to 100 parts by weight of component (A) from the viewpoint of adhesiveness.

Other additives can be added to the primer composition of the present invention in addition to the solvent, anti-aging agent, weather resistance improving agent, and filler. Examples of such other additives include physical property modifiers that adjust tensile properties of the cured film to be produced, storage stability improvers, radical inhibitors, metal deactivators, ozone degradation inhibitors, sagging inhibitors, and lubricants. , Pigments, foaming agents and the like. Specific examples of such additives are described in, for example, the specifications of Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Publication No. 2512468, and Japanese Patent Application Laid-Open No. 64-22904. Yes.

The primer composition of the present invention can be obtained by adding and mixing the above components.
The primer composition of the present invention can be coated on a substrate using a commonly employed coating method such as brush coating, spray coating, wire bar method, blade method, roll coating method, dipping method and the like.
The primer composition of the present invention can usually form a film at room temperature, but the film may be formed under various temperature conditions in order to adjust the film formation rate.

The primer composition of the present invention is effective when used as a primer for a sealing material mainly composed of a vinyl polymer having at least one crosslinkable silyl group, and in particular, a vinyl having at least one crosslinkable silyl group. When applied to a sealing material mainly composed of a polymer (for example, a sealing material mainly composed of a vinyl polymer disclosed in JP-A No. 11-80571), it is preferable because of good adhesiveness. Here, the “main component” means that the vinyl polymer accounts for 50% by weight or more of the whole polymer used for the sealing material.

The primer composition of the present invention includes various metals such as iron, stainless steel, aluminum, nickel, zinc, copper, acrylic resin, phenol resin, epoxy resin, polycarbonate resin, polybutylene terephthalate resin, alkali-treated fluorine resin, etc. synthetic resin materials, glass, ceramics, cement, inorganic materials mortar, and metamorphic silicone, silicone, polyurethane, acrylic urethane, polysulfide, metamorphic polysulfide, butyl rubber, acrylic, SBR-based, It is possible to firmly bond a fluorine-containing or isobutylene-based sealing material and a sealing material mainly composed of a vinyl polymer having at least one crosslinkable silyl group. Adhesiveness to silicone rubber such as a pre-stick silicone sealant that has been considered particularly difficult can be remarkably improved.

<Application>
The use of the primer composition of the present invention is not particularly limited, but it is an elastic sealant for construction, a sealant for multi-layer glass, an adhesive, an elastic adhesive, a coating material, a gasket, a casting material, various molding materials, and an artificial marble. , And anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), anti-vibration / vibration / soundproof / isolation materials used in automobiles, ships, home appliances, etc., automotive parts, electrical equipment It can be used as a primer for various applications such as liquid sealants used in parts and various machine parts. Among these, it can be more suitably used as a primer for adhesives, sealing materials, and liquid gaskets.

The primer composition of the present invention, when applied to a sealing material or the like mainly composed of a vinyl polymer having at least one crosslinkable silyl group, exhibits adhesion to various base materials and a silicone sealing material. Seamability and the like can be significantly improved.

The present invention will be described below based on examples, but is not limited to the following examples.
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; manufactured by Showa Denko) and chloroform as a GPC solvent were used.
Moreover, the viscosity of the polymer prepared in the synthesis example was measured at a temperature of 23 ° C. and 2 rpm using a BS viscometer manufactured by Tokimec Co., Ltd.

(Synthesis Example 1)
Synthesis of poly (n-butyl acrylate) having halogen at the terminal In a 50 ml flask, 0.63 g (4.4 mmol) of cuprous bromide, 0.76 g (4.4 mmol) of pentamethyldiethylenetriamine, 5 ml of acetonitrile, 2, 1.6 g (4.4 mmol) of diethyl 5-dibromoadipate and 44.7 g (349 mmol) of n-butyl acrylate were charged, freeze degassed, and then reacted at 70 ° C. for 7 hours in a nitrogen atmosphere. By removing and purifying the copper catalyst through an activated alumina column, a polymer having Br groups at the ends was obtained. The number average molecular weight of the obtained polymer was 10700, and the molecular weight distribution was 1.15.

Synthesis of poly (n-butyl acrylate) having an alkenyl group at the end 35 g of poly (n-butyl acrylate) having a Br group at the end obtained above in a 200 ml flask under nitrogen atmosphere, pentenoic acid Potassium 2.2 g (16.1 mmol) and N, N-dimethylacetamide (DMAc) 35 ml were charged and reacted at 70 ° C. for 4 hours. Unreacted potassium pentenoate and produced potassium bromide in the reaction mixture were removed by water extraction purification to obtain a polymer having an alkenyl group at the terminal. The number average molecular weight of the obtained polymer was 11300, and the molecular weight distribution was 1.12. The number of alkenyl groups per molecule of the polymer determined from ¹ H-NMR analysis was 1.82.

Synthesis of poly (n-butyl acrylate) having a crosslinkable silyl group at the end In a 200 ml pressure resistant reaction tube, 15 g of the polymer having an alkenyl group at the end obtained above, 1.8 ml (14.5 mmol) of methyldimethoxysilane, Methyl orthoformate 0.26 ml (2.4 mmol) and platinum bis (divinyltetramethyldisiloxane) 10 ⁻⁴ mmol were charged and reacted at 100 ° C. for 4 hours to obtain a polymer having a crosslinkable silyl group at the terminal. The viscosity of the obtained polymer was 44 Pa · s, the number average molecular weight was 11900, and the molecular weight distribution was 1.12. The number of crosslinkable silyl groups per molecule of the polymer determined by ¹ H-NMR analysis was 1.46.

(Synthesis Example 2)
Synthesis of hydroxyl-terminated polypropylene oxide 0.04 g of zinc hexacyanocobaltate-glyme complex, 2.0 g of dipropylene glycol in THF and 9.6 g of propylene oxide were added to the autoclave at 76 ° C under a nitrogen atmosphere. Reacted. Thereafter, 145.2 g of propylene oxide was added to the reaction system. Unreacted monomer and solvent were recovered and purified to obtain 150 g of oily product. The obtained product showed a single peak by GPC analysis, and the molecular weight distribution (Mw / Mn) was 1.14. The hydroxyl value was 11.8 mgKOH / g.

Synthesis of unsaturated group- terminated polypropylene oxide To 120 g of the hydroxyl group-terminated polypropylene oxide obtained above, 5.8 g (30.2 mmol) of a methanol solution of sodium methoxide (28 wt%) was added, and 130 ° C in an autoclave. And then devolatilized under reduced pressure. After returning to a nitrogen atmosphere, 2.8 g (36.2 mmol) of allyl chloride was added and reacted for 2 hours. The reaction mixture was dissolved in hexane, adsorbed with aluminum silicate, and then hexane was distilled off under reduced pressure to obtain unsaturated group-terminated polypropylene oxide.

The unsaturated group-terminated polypropylene oxide 120g obtained in Synthesis <br/> the crosslinkable silyl group-terminated polypropylene oxide were charged in a pressure glass reaction vessel, the isopropanol solution (25 g of chloroplatinic acid H ₂ PtCl 6 _· 6H after adding ₂ O what was dissolved in isopropanol 500 g) 0.02 g, and stirred for 30 minutes. Methyldimethoxysilane (2.1 g, 20.2 mmol) was added dropwise and reacted at 90 ° C. for 2 hours. Volatile components were removed by reducing the pressure to obtain a crosslinkable silyl group-terminated polypropylene oxide. The polymer had a viscosity of 6 Pa · s, a number average molecular weight of 17,300, and a molecular weight distribution of 1.14.

(Examples 1-4 and Comparative Examples 1-3)
Vinyl polymer having at least one crosslinkable silyl group of component (A) obtained in Synthesis Example 1, and γ- (2-aminoethyl) aminopropylmethyldimethoxysilane which is a silane coupling agent of component (B) (Nihon Unicar Co., Ltd., trade name: A-1120) or γ-isocyanatopropyltriethoxysilane (Nihon Unicar Co., Ltd., trade name: A-1310), (C) component silanol condensation catalyst Tetra-n-butyl titanate (produced by Wako Pure Chemical Industries, Ltd.), an organic titanate ester, or dibutyltin bisacetylacetonate (produced by Nitto Kasei Co., Ltd., trade name: Neostan), an organic tin compound U-220H), a hydroxyl group-containing silicone resin (made by Toray Dow Corning Co., Ltd., product name: 233FLAK, which is a silicone resin of component (D)) E) and n-hexane (manufactured by Wako Pure Chemical Industries, Ltd.) and toluene (manufactured by Wako Pure Chemical Industries, Ltd.) as solvents are mixed at a weight ratio shown in Table 1 below to prepare a primer composition. did.

(Example 5)
Vinyl polymer having at least one crosslinkable silyl group of component (A) obtained in Synthesis Example 1, and γ- (2-aminoethyl) aminopropylmethyldimethoxysilane which is a silane coupling agent of component (B) (Nihon Unicar Co., Ltd., trade name: A-1120) or γ-isocyanatopropyltriethoxysilane (Nihon Unicar Co., Ltd., trade name: A-1310), (C) component silanol condensation catalyst Tetra-n-butyl titanate (produced by Wako Pure Chemical Industries, Ltd.), an organic titanate ester, or dibutyltin bisacetylacetonate (produced by Nitto Kasei Co., Ltd., trade name: Neostan), an organic tin compound U-220H), a hydroxyl group-containing silicone resin (made by Toray Dow Corning Co., Ltd., product name: 233FLAK, which is a silicone resin of component (D)) E), a polyether polymer having at least one crosslinkable silyl group of component (E) obtained in Synthesis Example 2, and n-hexane (manufactured by Wako Pure Chemical Industries, Ltd.), toluene ( Wako Pure Chemical Industries, Ltd.) were mixed at a weight ratio shown in Table 1 below to prepare a primer composition.

On the other hand, a base material and a curing agent of a sealing material containing the vinyl polymer of the component (A) were prepared by the following method, and an adhesion test was performed using this sealing material.
With respect to 100 parts by weight of the vinyl polymer having at least one crosslinkable silyl group (A) obtained in Synthesis Example 1, diisodecyl phthalate (manufactured by Shin Nippon Rika Co., Ltd., trade name: SANSO) 50 parts by weight of sizer DIDP, 20 parts by weight of epoxy plasticizer (manufactured by Shin Nippon Rika Co., Ltd., trade name: Sanso Sizer E-PS), surface-treated colloidal calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., trade name: Haku Hana) CCR) 120 parts by weight, heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiten SB) 20 parts by weight, thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon 305) 2 parts by weight , 1 part by weight of a benzotriazole ultraviolet absorber (Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 327), a hindered amine light stabilizer (Sankyo Co., Ltd.) , Trade name: Sanol LS770) 1 part by weight, after interest each weighing, thoroughly kneading the mixture, and kneaded three times by a three-roll paint mill to obtain a main agent resulting composition.
In addition, tin octylate (manufactured by Nitto Kasei, trade name: U-28) / laurylamine (= 3 parts by weight / 0.75 part by weight), titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name: Taipei R-820) 10 parts by weight were weighed and mixed, and kneaded with a small homogenizer, and the resulting composition was used as a curing agent.

The adhesion test was performed and evaluated by the following method. Float glass compliant with JIS A-5758 (manufactured by Hiroshi Co., Ltd .: designated by Japan Sealant Industry Association, dimensions (cm): 5 × 5 × 0.5) is washed with acetone (manufactured by Wako Pure Chemical Industries, Ltd.) Then, the primer composition shown in Table 1 was applied once. In addition, fully cured and cured silicone sealing material with dimensions of 4x3x10 (GE Toshiba Silicone Co., Ltd., trade name: Tosseal 361) is cut into two with a cutter knife. (Dimension (cm): 2 × 3 × 10), and the cut surface was washed with toluene (manufactured by Wako Pure Chemical Industries, Ltd.), and then the primer composition shown in Table 1 was applied once. The mixture was allowed to stand at 23 ° C. for 30 minutes or longer, and the main component and the curing agent of the above-mentioned vinyl polymer sealing material were weighed in a weight ratio of main component / curing agent = 100/10 and sufficiently kneaded on each primer layer formed with a film. The material was applied at a thickness of 5 mm and cured at room temperature (23 ° C.). All curing conditions are 23 ° C. × 7 days. After curing, an incision was made on the adhesive surface, the incision site was grasped by hand, and a hand peeling test was performed while cutting the adhesive interface with a cutter knife while pulling at about 90 degrees. The surface of the peeled substrate was observed, and the area ratio of the cohesive failure portion with respect to the entire adhesion surface was defined as the cohesive failure rate (%). Table 1 shows the composition of the primer composition and the measurement results of the adhesion test.

The primer composition of the present invention, when applied to a sealing material or the like mainly composed of a vinyl polymer having at least one crosslinkable silyl group, exhibits adhesion to various base materials and a silicone sealing material. Seamability and the like can be significantly improved.

Claims (12)

(A) Vinyl polymer having at least one crosslinkable silyl group represented by the 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 the same or different and are each 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. A triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). When two or more 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 Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. },
(B) a silane coupling agent, and
(C) a primer composition comprising a silanol condensation catalyst ,
A primer composition for joining to the surface of a silicone sealant . The primer composition according to claim 1, further comprising (D) a silicone resin. The primer composition according to claim 1, further comprising (E) a polyether polymer having at least one crosslinkable silyl group represented by the 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 the same or different and are each 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. A triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). When two or more 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 Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. } The primer composition according to any one of claims 1 to 3, wherein the (C) silanol condensation catalyst is an organic tin compound and / or an organic titanate. The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the vinyl polymer of component (A) is less than 1.8. The primer composition according to any one of the above. The primer composition according to any one of claims 1 to 5, wherein the main chain of the vinyl polymer (A) is a (meth) acrylic polymer. The primer composition according to any one of claims 1 to 6, wherein the main chain of the vinyl polymer (A) is produced by a living radical polymerization method. The primer composition according to any one of claims 1 to 7, wherein the main chain of the vinyl polymer (A) is produced by an atom transfer radical polymerization method. The vinyl polymer of the component (A) has at least one crosslinkable silyl group represented by the general formula (1) at the molecular chain terminal, according to any one of claims 1 to 8. Primer composition. The vinyl polymer as the component (A) has the following steps:
(1) An organic halide or a sulfonyl halide compound is used as an initiator, and a vinyl monomer is radically polymerized using a transition metal complex as a catalyst to produce a vinyl polymer having a halogen at its terminal,
(2) A vinyl polymer having an alkenyl group at the terminal is produced by reacting an oxyanion having an alkenyl group to replace halogen.
(3) reacting a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1);
The primer composition of any one of Claims 1-9 which is a polymer obtained by these. The primer composition according to any one of claims 2 to 10, wherein the main chain of the polyether-based polymer (E) is essentially polypropylene oxide. (B) The primer composition of any one of Claims 1-11 whose silane coupling agent of a component is an amino group containing silane coupling agent.