JP2000129199A - Primer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a primer composition enabling the amount of a solvent used therefor to be reduced, capable of affording the corresponding cured product of high heat resistance and weatherability, and useful as e.g. an elastic sealant intended for construction by including a vinyl-based polymer having specific crosslinkable silyl group. SOLUTION: This primer composition comprises a vinyl-based polymer such as (meth)acrylic polymer having at least one crosslinkable silyl group of the formula [R1 and R2 are each a 1-20C alkyl, 6-20C aryl, 7-20C aralkyl or (R')3SiO (R' is a 1-20C univalent hydrocarbon group); Y is hydroxy group or a hydrolyzable group; (a) is 0-3; (b) is 0-2; (m) is 0-19; wherein (a+mb)>=1]; wherein it is preferable that the vinyl-based polymer is obtained by living radical polymerization process, the ratio: weight-average molecular weight/number-average molecular weight for the polymer determined by gel permeation chromatography being <1.8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a primer composition. More specifically, various elastic sealing materials or elastic adhesives, elastic sealing materials, rubber, mortar,
The present invention relates to a primer composition effective for bonding to metals, ceramics, glass, cement, ceramic moldings, plastics, and various painted surfaces.

[0002]

2. Description of the Related Art In recent years, elastic sealing materials or elastic adhesives have been widely used in architectural or industrial applications. However, these adhesive performances are not versatile, and especially when durability is emphasized, the use of a primer is almost indispensable in order to secure the adhesive reliability.

[0003]

In recent years, there has been an increasing awareness of the working environment and environmental pollution, and the use of solvents for primers has been regarded as a problem for primers. In addition, non-priming without using a primer is expected.

[0004] However, the non-priming method has a concern that a peeling trouble due to a variation in adhesiveness is a concern, and the water-based primer method has been partially advanced, but the performance is still insufficient. Since the primer improves the wettability to the adherend, the composition is more preferably low in viscosity. Examples of using a (meth) acrylic polymer having a crosslinkable silyl group as a primer include, for example, JP-A-7-11199, but these polymers are synthesized using free radical polymerization, and thus have a molecular weight distribution. As a result, the viscosity of the polymer and the viscosity of the primer composition using the polymer become high, and there is a problem that a large amount of solvent must be used.

In order to solve this problem, it is necessary to reduce the viscosity of a vinyl polymer having a crosslinkable silyl group, and there is a method of reducing the molecular weight of the polymer. However, when the molecular weight is reduced, the interval between the cross-linking points of the cured product becomes shorter, and the cross-linking density becomes extremely high. As a result, the obtained primer is extremely poor in elastic properties and causes problems such as destruction of the primer itself or peeling between the primer and the adherend, which is not an appropriate method.

As another method, the molecular weight distribution of a vinyl or (meth) acrylic polymer, that is, the ratio (Mw / Mw) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography.
A method of reducing the amount of solvent used by reducing n) and lowering the viscosity of the polymer may be considered. However, until now, vinyl type or (meth) with narrow molecular weight distribution
It was not easy to obtain an acrylic polymer.

If a (meth) acrylic polymer having a crosslinkable silyl group having a narrow molecular weight distribution can be obtained, the amount of solvent used can be reduced and these problems can be solved.

Further, for example, a vinyl polymer having a crosslinkable silyl group or a cured product obtained from a composition thereof is excellent in heat resistance or weather resistance. Paints, coating materials, can be used for various applications such as sealing materials, but since the primer composition of the present invention has a structure similar to these polymers, it has good compatibility with them,
Suitable as a primer.

[0009]

Means for Solving the Problems It has been found that the above problems can be solved by using a vinyl polymer having at least one crosslinkable silyl group as a main component of the primer composition, and the present invention has been achieved.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is a primer composition containing 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 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 SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′s may be the same or different) It represents a triorganosiloxy group, and 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,
When two or more Ys are present, they may be the same or different. a is 0, 1, 2, or 3
And b represents 0, 1, or 2. m is 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied.加 水 The hydrolyzable group represented by Y is not particularly limited, and conventionally known groups can be used. Specifically,
Hydrogen, a halogen atom, an alkoxy group, an acyloxy group,
Ketoximate group, amino group, amide group, aminooxy group, mercapto group, alkenyloxy group and the like,
In terms of mild hydrolysis and easy handling,
Alkoxy groups are particularly preferred. The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 and a + mb, that is, the sum of the hydrolyzable groups is 1 to
A range of 5 is preferred. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different. The number of silicon atoms constituting the crosslinkable silicon compound may be one, or two or more. In the case of silicon atoms linked by a siloxane bond, the number may be up to about 20.

The content of the vinyl polymer having at least one crosslinkable silyl group of the general formula (1) in the primer composition of the present invention is usually 2% by weight or more, and 10% by weight or more. Is preferred.

The monomer constituting the main chain of the vinyl polymer having at least one crosslinkable silyl group of the general formula (1) is not particularly limited, and various monomers can be used. The vinyl monomer used for producing the main chain of the vinyl polymer of the present invention is not particularly limited, and various types can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, -n (meth) acrylate
-N-butyl, isobutyl (meth) acrylate, -tert-butyl (meth) acrylate, -n-pentyl (meth) acrylate, -n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, ( (Meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl,
Dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth)
2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, (meth)
2-perfluoroethyl acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, (meth) acryl (Meth) acrylic monomers such as 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate; styrene, vinyltoluene, α-methyl Styrene monomers such as styrene, chlorostyrene, styrene 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 Monomer; anhydrous Maleic acid, maleic acid, monoalkyl esters and dialkyl esters of maleic acid;
Fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide,
Maleimide monomers such as hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl monomers having a nitrile group such as acrylonitrile and methacrylonitrile; vinyl monomers having an amide group such as acrylamide and methacrylamide; Vinyl acetates such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate 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 can be mentioned. These may be used alone or a plurality of them may be copolymerized. In the above expression format, for example, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

A vinyl polymer having at least one crosslinkable silyl group of the general formula (1), which is obtained by synthesizing at least 40% by weight of a (meth) acrylic acid monomer among the above monomers. A (meth) acrylic polymer is more preferable in terms of physical properties.

The molecular weight of the vinyl polymer having at least one crosslinkable silyl group is not particularly limited.
It is preferably in the range of 100 to 100,000. When the molecular weight is 500 or less, the intrinsic properties of the vinyl polymer are hardly exhibited, and when it is 100,000 or more, handling becomes difficult.

The molecular weight distribution of the vinyl polymer having at least one crosslinkable silyl group, that is, the weight average molecular weight (M) measured by gel permeation chromatography
The ratio (Mw / Mn) of w) 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 of the primer composition low and to facilitate the handling and to obtain a sufficient function. The value of the molecular weight distribution is preferably less than 1.8, more preferably 1.7 or less, further preferably 1.6 or less, further preferably 1.5 or less, still more preferably 1.4 or less, and still more preferably 1. 3 or less.

The vinyl polymer having at least one crosslinkable silyl group can be obtained by various polymerization methods.
The method is not particularly limited. However, from the viewpoint of versatility and controllability of the monomer, it has a specific functional group that can be directly introduced into a crosslinkable silyl group by a radical polymerization method or converted into a crosslinkable silyl group in one or several steps of reaction. A more preferred method is to obtain a vinyl polymer and convert this specific functional group into a crosslinkable silyl group to obtain a vinyl polymer having at least one crosslinkable silyl group.

A method for producing a vinyl polymer having a specific functional group containing a crosslinkable silyl group by a radical polymerization method is as follows.
When a vinyl monomer is polymerized using an azo compound or a peroxide as a polymerization initiator, a `` general radical polymerization method '' in which a monomer having a specific functional group is simply copolymerized and a specific functional group is terminated. Can be classified as a "controlled radical polymerization method" in which the compound is introduced at a controlled position.

The "controlled radical polymerization method" includes a "chain transfer agent method" in which a vinyl polymer having a functional group at a terminal is obtained by using a chain transfer agent having a specific functional group, and a terminating reaction at the terminal of the initiator. It can be classified as a "living radical polymerization method" in which a polymer having a molecular weight almost as designed is obtained by growing without causing the polymerization.

The "general radical polymerization method" is a simple method and can be used in the present invention. However, since a monomer having a specific functional group is introduced into the polymer only stochastically, the In order to obtain a polymer having a high functional group, it is necessary to use a considerably large amount of this monomer.On the contrary, a small amount of the polymer in which the specific functional group is not introduced becomes large. Although it is possible to obtain a polymer having the same, there are problems.

In the "chain transfer agent method", it is possible to obtain a polymer having a high functionalization rate, and it can be used in the present invention. A chain transfer agent having a functional group is required, and there is a problem in terms of economy including treatment. Further, similarly to 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.

In a narrow sense, living polymerization refers to polymerization in which the terminal is constantly active and the molecular chain grows. In general, however, those in which the terminal is inactivated and those in which the terminal is activated are Pseudo-living polymerization that grows in a state of equilibrium is also included. The definition in the present invention is also the latter. In recent years, various groups have been actively studying the "living radical polymerization method". Examples thereof include a cobalt porphyrin complex (J. Am. Chem. Soc.
(1994, 116, 7943) and those using a radical scavenger such as a nitroxide compound (Macromole)
Cules, 1994, 27, 7228), "Atom Transfer Radical Polymerization" using an organic halide or the like as an initiator and a transition metal complex as a catalyst (Atom Transfer R)
digital Polymerization: AT
RP). Polymerization rate is high, termination reaction due to coupling between radicals etc. is easy to occur,
Although the radical polymerization is difficult to control, the termination reaction does not easily occur in living radical polymerization, so that a polymer having a narrow molecular weight distribution (Mw / Mn = 1.1 to 1.5) can be obtained, The molecular weight can be freely controlled by adjusting the ratio of the charged agents.

In the "living radical polymerization method", a polymer having a narrow molecular weight distribution and a low viscosity can be obtained due to its characteristics, and a monomer having a specific functional group is introduced into almost any position of the polymer. Since it is possible, it is more preferable as a method for producing a vinyl polymer having a specific functional group.

Among the "living radical polymerization methods", an "atom transfer radical polymerization method" in which an organic halide or a sulfonyl halide compound is used as an initiator and a transition metal complex is used as a catalyst to polymerize a vinyl monomer (for example, Mat
yjaszewski et al. Am. Chem. So
c. 1995, 117, 5614, Macromole
cules 1995, 28, 7901, Sciencec
e 1996, 272, 866 or Sawamo
To et al., Macromolecules 1995, 2
No. 8,1721) has, in addition to the features of the above-mentioned "living radical polymerization method", a terminal having a halogen or the like which is relatively advantageous for a functional group conversion reaction, and has a high degree of freedom in designing an initiator and a catalyst. For this reason, the method for producing a vinyl polymer having a specific functional group is more preferable.

In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl position), Alternatively, a sulfonyl halide compound is used as an initiator.

As the transition metal complex used as a catalyst for the above atom transfer radical polymerization, groups 7 and 8 of the periodic table,
A complex including a Group 9, Group 10, or Group 11 element as a central metal can be used. Preferred are 0-valent copper, 1
Complex of divalent copper, divalent ruthenium, divalent iron or divalent nickel. Among them, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. is there. When a copper compound is used, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine and the like for enhancing the catalytic activity A ligand such as a polyamine is added. 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, aluminum alkoxides are added as an activator. Further, bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ) and bistriphenylphosphine complex of divalent nickel (NiCl ₂ (PP
h _{3) 2),} and a divalent bis tributylphosphine complex nickel _{(NiBr 2 (PBu 3) 2} ) are also suitable as catalysts.

There are no particular restrictions on the vinyl monomer used in this polymerization, and any of those already exemplified can be suitably used.

The above polymerization reaction can be carried out without a solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene; diethyl ether;
Ether solvents such as tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, propanol, isopropanol, n-butyl alcohol, ter
alcohol solvents such as t-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate. These can be used alone or in combination of two or more. The polymerization can be carried out at a temperature in the range of 0 to 200 ° C, and preferably in the range of room temperature to 150 ° C.

The vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1) can be obtained by the following method, but is not limited thereto. .

As a method for synthesizing a vinyl polymer having at least one crosslinkable silyl group, (A) a hydrosilane compound having a crosslinkable silyl group in a vinyl polymer having at least one alkenyl group may be prepared using a hydrosilylation catalyst. (B) a method of reacting a vinyl polymer having at least one hydroxyl group with a compound having a group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group in one molecule (C) When synthesizing a vinyl polymer by radical polymerization, a method of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule (D) When synthesizing a vinyl polymer by radical polymerization, Method using a chain transfer agent having a crosslinkable silyl group (E) Vinyl having at least one highly reactive carbon-halogen bond A method of reacting a compound having a stable carbanion and crosslinkable silyl group in a molecule in the polymer; and the like.

The vinyl polymer having at least one alkenyl group used in the method (A) can be obtained by various methods. The synthesis method is illustrated below, but is not limited thereto.

(Aa) When a vinyl polymer is synthesized by radical polymerization, for example, a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula (2) A compound having the following as a second monomer: ^{_{H 2 C = C (R 3}} ) -R 4 -R 5 -C (R 6) = CH
₂ (2) (wherein, R ³ represents hydrogen or a methyl group, and R ⁴ represents —C
(O) O-, or o-, m-, shows a p- phenylene group, R ⁵ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms, contain one or more ether bonds May be. R ⁶ is hydrogen or an alkyl group having 1 to 10 carbon atoms;
It represents an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.) There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. In particular, in the case of living radical polymerization, when a rubber-like property is expected, it is preferable to react as a second monomer at the end of the polymerization reaction or after the reaction of a predetermined monomer is completed.

(Ab) In the synthesis of a vinyl polymer by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1, A method of reacting a compound having at least two alkenyl groups having low polymerizability such as 9-decadiene.

(Ac) The vinyl polymer having at least one highly reactive carbon-halogen bond includes, for example, various organic compounds having an alkenyl group such as organic tin such as allyltributyltin and allyltrioctyltin. A method in which a halogen is substituted by reacting a metal compound.

(Ad) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having an alkenyl group as shown in the general formula (3) to form a halogen. How to replace. ^{M + C - (R 7)} (R 8) 9 -C (R 6) = CH 2 (3) ( wherein -R, R ⁶ are as defined above, R ^7, R ⁸ are both carbanion C ^- stable R ⁹ represents a direct bond or a C 1-10 alkyl group, or one of the above electron withdrawing groups and the other one of hydrogen or an alkyl group having 1 to 10 carbon atoms, or a phenyl group. Represents an organic group of valence, and may contain one or more ether bonds. M ⁺ represents an alkali metal ion or a quaternary ammonium ion.) The electron-withdrawing groups of R ⁷ and R ⁸ include —CO ₂ R, -C
Those having the structure of (O) R and -CN are particularly preferred.

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

(Af) The vinyl polymer having at least one highly reactive carbon-halogen bond may be, for example, an oxyanion or carboxy having an alkenyl group represented by the general formula (4) or (5). A method in which a halogen is substituted by reacting a rate anion. ^{_{H 2 C = C (R 6}} ) -R 10 -O - M + (4) ( wherein, R ^6, M ⁺ is the same .R ¹⁰ in the 1 to 20 carbon atoms
A divalent organic group may contain one or more ether _{bonds) H 2 C = C (R} 6) -R 11 -C (O) O of ^- M ⁺ (5) (wherein, R ⁶ , M ⁺ are the same as described above, and R ¹¹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms, which may contain one or more ether bonds.

The above-mentioned method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond is described, for example, in (Ea) Radical polymerization in JP-A-4-13270.
6, a method using a halide such as carbon tetrachloride, ethylene chloride, carbon tetrabromide, or methylene bromide as a chain transfer agent (chain transfer agent method).

(Eb) An atom transfer radical polymerization method using an organic halide as described above as an initiator and a transition metal complex as a catalyst; and the like, but is not limited thereto.

The vinyl polymer having at least one alkenyl group can also be obtained from a vinyl polymer having at least one hydroxyl group, and the following exemplified methods can be used. is not.
(Ag) A method in which a base such as sodium methoxide is allowed to act on a hydroxyl group of a vinyl polymer having at least one hydroxyl group to react with a alkenyl group-containing halide such as allyl chloride.

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

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

(Aj) a method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst;

In the present invention, when a halogen is not directly involved in the method for introducing an alkenyl group such as (Aa) or (Ab), a vinyl polymer is synthesized by a living radical polymerization method. Is preferred. The method (Ab) is more preferable because the control is easier.

When an alkenyl group is introduced by converting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halogen having at least one highly reactive carbon-halogen bond may be used. Halide, or a sulfonyl halide compound as an initiator,
Obtained by radical polymerization of a vinyl monomer using a transition metal complex as a catalyst (atom transfer radical polymerization method).
At least one highly reactive carbon-halogen bond at the terminal
It is preferable to use a vinyl polymer having two or more vinyl polymers. The method (Af) is more preferable because the control is easier.

The hydrosilane compound having a crosslinkable silyl group is not particularly limited, but a typical example is a compound represented by the general formula (6). _{^{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 described above.) Among these hydrosilane compounds, particularly, the general formula (7) H—Si (R ² ) _3-a (Y) _a (7) (wherein R ² , Y, and a are the same as those described above).

When the above-mentioned hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. As the transition metal catalyst, for example, platinum alone, alumina, silica, a dispersion of platinum solids on a carrier such as carbon black, chloroplatinic acid, a complex of chloroplatinic acid with alcohol, aldehyde, ketone, etc.
Platinum-olefin complexes and platinum (0) -divinyltetramethyldisiloxane complexes are exemplified. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ and RhC
l ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , Al
Cl ₃ , PdCl ₂ · H ₂ O, NiCl ₂ , TiCl
_{4 and the} like.

The method for producing the vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) is exemplified by the following methods. However, the present invention is not limited to this.

(Ba) When a vinyl polymer is synthesized by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula (8) may be used. A method of reacting as monomer 2. H ₂ C ＝ C (R ³ ) —R ⁴ —R ⁵ —OH (8) (wherein R ³ , R ⁴ and R ⁵ are the same as above) A polymerizable alkenyl group and a hydroxyl group in one molecule There is no limitation on the timing of reacting the compound having the above. Particularly, in the case of living radical polymerization, when a rubber-like property is expected, the reaction is carried out as the second monomer at the end of the polymerization reaction or after the completion of the reaction of a predetermined monomer. Is preferred.

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

(Bc) For example, JP-A-5-262808
A radical polymerization of a vinyl monomer using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide shown in (1).

(Bd) For example, JP-A-6-23991
2. A method of radically polymerizing a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as described in JP-A-8-283310.

(Be) For example, JP-A-6-116312
A method of radically polymerizing a vinyl monomer by using an excess of alcohols as described in (1).

(Bf) For example, JP-A-4-132706
A method of introducing a hydroxyl group into a terminal by hydrolyzing or reacting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond with a hydroxyl group-containing compound by a method such as that described in US Pat.

(Bg) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group as shown in the general formula (9) to substitute halogen. how to. ^{M + C - (R 7)} (R 8) -R 9 -OH (9) as the electron withdrawing group ^{(wherein, R 7, R 8, R} 9, the same is) R ^7, R ⁸ is -CO ₂ R, -C
Those having the structure of (O) R and -CN are particularly preferred.

(Bh) An enolate anion is prepared by treating a vinyl polymer having at least one highly reactive carbon-halogen bond with a simple metal such as zinc or an organometallic compound. A method of reacting aldehydes or ketones later.

(Bi) A vinyl polymer having at least one highly reactive carbon-halogen bond may be added to a hydroxyl group-containing oxyanion or carboxylate represented by the general formula (10) or (11). A method in which halogen is substituted by reacting an anion. ^{HO-R 10 -O - M +} (10) ( wherein, R ¹⁰ and M ⁺ are the ^{same) HO-R 11 -C (O} ) O - M + (11) ( wherein, R ¹¹ and M ⁺ Is the same as described above).

In the present invention, when a halogen is not directly involved in the method for introducing a hydroxyl group such as (Ba) to (Be), a vinyl polymer is synthesized by using a living radical polymerization method. Is preferred. The method (Bb) is more preferable because the control is easier.

When a hydroxyl group is introduced by converting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide,
Alternatively, a vinyl-based compound having at least one highly reactive carbon-halogen bond at a terminal obtained by radically polymerizing a vinyl-based monomer using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization method). Preferably, a polymer is used. The method (Bi) is more preferable because the control is easier.

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

Examples of the compound having a polymerizable alkenyl group and a crosslinkable silyl group in one molecule used in the method (C) include, for example, trimethoxysilylpropyl (meth) acrylate and methyldimethoxysilylpropyl (meth) acrylate. Such a compound represented by the following general formula (12) is exemplified. ^{_{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, m is Same as above. R ¹² may be a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.) A polymerizable alkenyl group and a crosslinkable group in one molecule. There is no particular limitation on the timing of reacting a compound having a silyl group. Particularly, in the case of living radical polymerization, when a rubber-like property is expected, the second monomer is used as the second monomer at the end of the polymerization reaction or after the reaction of a predetermined monomer is completed. It is preferred to react.

As the chain transfer agent having a crosslinkable silyl group used in the chain transfer agent method (D), for example,
And mercaptans having a crosslinkable silyl group, hydrosilanes having a crosslinkable silyl group, and the like, which are described in JP-B-14068 and JP-B-4-55444.

The vinyl polymer having at least one highly reactive carbon-halogen bond used in the method (E) can be obtained by the methods (Ea) to (Eb) as described above. it can. As a compound having both a crosslinkable silyl group and a stabilized carbanion in one molecule, a compound represented by the general formula (13) can be given. ^{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, and m are the same as described above. R ¹³ is a direct bond or a group having 1 to 1 carbon atoms. R ¹⁴ may be hydrogen or an alkyl group having 1 to 10 carbon atoms, wherein the divalent organic group may have one or more ether bonds.
An aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms is shown. ) The electron-withdrawing groups for R ⁷ and R ⁸ include —CO ₂ R and —C
Those having the structure of (O) R and -CN are particularly preferred.

Further, a vinyl polymer having at least one crosslinkable silyl group at the terminal of the molecular chain is obtained by a polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. It is preferable to use an organic halide having two or more highly reactive carbon-halogen bonds as starting points or a sulfonyl halide compound as an initiator. As specific examples of them,

[0064]

Embedded image (Wherein, R is an alkyl group having 1 to 20 carbon atoms, 6 to
Represents an 20 aryl group or an aralkyl group having 7 to 20 carbon atoms. C ₆ H ₄ represents a phenylene group. n represents an integer of 0 to 20. X represents chlorine, bromine, or iodine. )

[0065]

Embedded image (Wherein, X represents chlorine, bromine or iodine.
Represents an integer of 20. C ₆ H ₄ represents a phenylene group. )
And the like.

A vinyl polymer having at least one crosslinkable silyl group at the terminal of the molecular chain can be obtained in addition to the above.

When an organic halide having a crosslinkable silyl group is used as an initiator, a vinyl polymer having a crosslinkable silyl group at one terminal and the other terminal having the structure of the general formula 2 can be obtained. By converting the halogen at the terminal end of the polymer thus obtained into a crosslinkable silyl group-containing substituent,
A vinyl polymer having a crosslinkable silyl group at both ends can be obtained. As the conversion method, the method already described can be used.

Organic halide having crosslinkable silyl group
Is not particularly limited, for example, general formula (14):
One having the structure shown in (15) is exemplified. R^FifteenR¹⁶C (X) -R¹⁷-R¹⁸-C (H) (R¹⁹) CH
_Two− [Si (R¹)_2-b(Y)_bO]_m-Si (R^Two)
_3-a(Y)_a(14) (where R¹, R^Two, A, b, m, X and Y are the same as above.
R^Fifteen, R¹⁶Is independently hydrogen or C 1-20
An alkyl group, an aryl group having 6 to 20 carbon atoms, or carbon
Aralkyl groups of the formulas 7 to 20, or mutually at the other end
Concatenated, R ¹⁷Is -C (O) O-, -C (O)-,
Alternatively, it represents an o-, m-, p-phenylene group. R¹⁸Is
1 direct bond, or a divalent organic group having 1 to 10 carbon atoms
R which may contain the above ether bond,¹⁹Is hydrogen,
Or an alkyl group having 1 to 10 carbon atoms and 6 to 10 carbon atoms
Represents an aryl group or an aralkyl group having 7 to 10 carbon atoms
You. ) (R^Two)_3-a(Y)_aSi- [OSi (R¹)_2-b(Y)_b]
_m-CH_Two-C (H) (R ¹⁹) -R¹⁸-C (R^Fifteen) (X)
-R¹⁷-R¹⁶ (15) (where R¹, R^Two, R^Fifteen, R¹⁶, R¹⁷, R¹⁸, R¹⁹,
a, b, m, X, and Y are the same as described above.) An organic halide having a crosslinkable silyl group is used as an initiator.
When used, one end is a crosslinkable silyl group and the other end is a halo.
To obtain a polymer,
A total of two or more identical or different functional groups
Using the compound above, cup the halogen terminals
By cross-linking, both ends are crosslinkable silyl groups
Can be obtained.

The compound having two or more identical or different functional groups capable of substituting a terminal halogen is not particularly limited, but includes polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof, alkali metal sulfides and the like. Is preferred.

When an organic halide having an alkenyl group is used as the initiator, a polymer having an alkenyl group at one terminal and a halogen at the other terminal is obtained. By converting the halogen at the terminal of the polymer thus obtained into an alkenyl-containing substituent, a vinyl polymer having an alkenyl group at both terminals can be obtained. By converting to a silyl group, a vinyl polymer having a crosslinkable silyl group at both terminals can be obtained.

When the adherend has a large amount of deformation such as an elastic sealing material or rubber, the molecular weight between cross-linking points, which greatly affects rubber elasticity, is increased.
It is preferable to form a soft primer layer. For that purpose, at least one of the crosslinkable silyl groups is preferably at the terminal of the molecular chain, and more preferably all of them are at the terminal of the molecular chain.

Accordingly, a hydroxyl group, which is used when synthesizing a vinyl polymer having at least one crosslinkable silyl group,
The vinyl polymer having at least one halogen or alkenyl group preferably has these functional groups at the terminal of the molecular chain.

A method for producing a vinyl polymer having at least one crosslinkable silyl group, in particular, a (meth) acrylic polymer is described in, for example, JP-B-3-14068 and JP-B-4-14.
55544 and JP-A-6-219922. Since these methods use the "chain transfer agent method", these crosslinkable silyl groups are present at a relatively high ratio at the terminal. The molecular weight distribution of the resulting polymer is generally as wide 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, a low viscosity and a high proportion of a crosslinkable silyl group at a terminal, it is preferable to use a living radical polymerization method.

In curing the primer composition of the present invention, a condensation catalyst may or may not be used. Titanate such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dimethoxide, dibutyltin oxide and carboxylic acid ester or carboxylic acid Or a reactant of a hydroxyl group-containing compound,
Organotin compounds such as tin octylate and tin naphthenate; organic aluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate zirconium tetraisopropoxide; zirconium Organic zirconium compounds such as tetrabutoxide; organic lead compounds such as lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine , Benzylamine, diethylaminopropylamine, xylylenediamine, triethylenedi Min, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N- methylmorpholine,
1,3-diazabicyclo (5,4,6) undecene-7
Amine compounds and their carboxylate salts; reaction products and mixtures of amine compounds and organotin compounds such as a reaction product or mixture of laurylamine and tin octylate; obtained from excess polyamine and polybasic acid Low molecular weight polyamide resin; reaction product of excess polyamine and epoxy compound; silane coupling agent having amino group, for example, γ-aminopropyltrimethoxysilane;
One or more known silanol catalysts such as N- (β-aminoethyl) aminopropylmethyldimethoxysilane may be used as necessary. The amount used is 0 based on the (meth) acrylic polymer having a crosslinkable silyl group at the terminal.
It is preferred to use from 10 to 10% by weight. Hydrolysable group Y
When an alkoxy group is used as the polymer, a curing catalyst is preferably used because the curing speed is slow only with this polymer.

As the adhesion promoter, the polymer itself according to the present invention has an adhesive property to an elastic sealing material, rubber, mortar, metal, ceramics, glass, cement, ceramic molding, plastic, and various painted surfaces. Although it is not always necessary, it is preferably used in order to obtain stable adhesion to various adherends.

Examples of the adhesion promoter include phenolic compounds such as phenol, cresol, xylenol, resorcinol, alkylphenol, and modified phenols (for example, cashew oil-modified phenol and tall oil-modified phenol) and aldehyde compounds such as formalin and paraformaldehyde. Resol type or novolak type phenolic resin obtained by the reaction with
Bisphenol A epoxy resin, bisphenol F
Resins such as epoxy resin, novolak epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, hydrogenated bisphenol A type epoxy resin; alkyl titanates such as tetrabutyl titanate; tolylene diisocyanate, diphenylmethane diisocyanate, etc. Aromatic polyisocyanate of γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-
Compounds having an amino group and a crosslinkable silyl group in one molecule, such as (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; γ Compounds having an epoxy group and a crosslinkable silyl group in one molecule, such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane; γ-mercaptopropyl Compounds having a mercapto group and a crosslinkable silyl group in one molecule such as trimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanate Propyltriethoxysilane, γ-iso A compound having an isocyanate group and a crosslinkable silyl group in one molecule such as anatopropylmethyldimethoxysilane; a compound having an amino group and a crosslinkable silyl group and a compound having an epoxy group in one molecule; A compound having an epoxy group and a crosslinkable silyl group in a molecule or a reaction product of a compound having an isocyanate group and a crosslinkable silyl group in a molecule; γ- (meth) acryloxypropyltrimethoxysilane, γ-
(Meth) acryloxypropyltriethoxysilane, γ
Reaction of a compound having a (meth) acryloxy group and a crosslinkable silyl group in one molecule such as (meth) acryloxypropylmethyldimethoxysilane and a compound having an amino group and a crosslinkable silyl group in one molecule as described above Object; and the like. These may be used alone or in combination of two or more. Among them, compounds having amino group and crosslinkable silyl group in one molecule, compounds having epoxy group and crosslinkable silyl group in one molecule, and mercapto group crosslinkable in one molecule, whose physical properties and adhesion are relatively easy to control A compound having a silyl group, a compound having an amino group and a crosslinkable silyl group in one molecule and a compound having an epoxy group, or a reaction product of a compound having an epoxy group and a crosslinkable silyl group in one molecule, (meth) acryloxy in one molecule An organic group having at least one of nitrogen, oxygen and sulfur atoms in one molecule such as a compound having a group and a crosslinkable silyl group and a reaction product of a compound having an amino group and a crosslinkable silyl group in one molecule; Compounds having a crosslinkable silyl group are preferred. The organic group having at least one of the above-mentioned nitrogen, oxygen and sulfur atoms is an amino group, an isocyanate group or a group formed by a reaction of these groups. Compounds having an organic group having an atom and a crosslinkable silyl group are more preferred.

The adhesion promoter is used with respect to 100 parts by weight of a vinyl polymer having at least one crosslinkable silyl group.
It is preferred to use from 0.01 to 20 parts by weight. 0.
When the amount is less than 01 parts by weight, the effect of improving the adhesiveness is hardly exhibited,
If it exceeds 20 parts by weight, the physical properties of the cured product are adversely affected. The addition amount of the adhesion promoter is preferably 0.1 to 10 parts by weight,
More preferably, it is 0.5 to 5 parts by weight.

Various solvents may be used to adjust workability and wettability to an adherend. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane and cyclohexane; alcohol solvents such as methanol, ethanol and isopropanol; ethyl acetate, butyl acetate, amyl acetate; Ester solvents such as cellosolve acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone; These solvents may be used during the production of the polymer. When a polar solvent such as an alcohol-based solvent, an ester-based solvent, or a ketone-based solvent is used, the adhesive performance on a wet surface can be improved.
In order to control the physical properties by increasing the hardness when the primer composition is cured or lowering the hardness and extending the elongation,
A physical property modifier can be used.

Examples of the physical property modifier include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ
-Alkylisopropenoxysilanes such as glycidoxypropylmethyldiisopropenoxysilane; various silane coupling agents such as vinyltrimethoxysilane and vinylmethyldimethoxysilane; silicone varnishes; and polysiloxanes as required. Is added. A preferable result can be obtained by adding 0 to 20 parts by weight based on 100 parts by weight of the vinyl polymer having at least one crosslinkable silyl group.

To increase the curing speed of the primer composition,
A curability modifier can be added to retard the composition, and a storage stability improver can be added to suppress the increase in viscosity during storage. Alcohols such as methanol and ethanol; and methyl nadono orthoesters of orthoformate; compounds having a crosslinkable silyl group such as tetraethoxysilane, methyltrimethoxysilane and vinyltrimethoxysilane as curability modifiers or storage stability improvers Carboxylic acids such as 2-ethylhexanoic acid; Vinyl polymer 1 having at least one crosslinkable silyl group
A preferable result can be obtained by adding 0 to 20 parts by weight with respect to 00 parts by weight.

The primer composition of the present invention may further include various fillers such as silica, carbon black and calcium carbonate; aromatic dibasic acid esters such as di (2-ethylhexyl) phthalate; and non-aromatics such as dioctyl adipate. Dibasic acid esters; polyethers such as polypropylene glycol, various plasticizers such as acrylic oligomers; various silane coupling agents, various modifiers such as polysiloxane having a crosslinkable silyl group; polyamide wax, hydrogenated castor oil And rheological property modifiers such as metal soaps; surface property and / or weatherability modifiers such as ultraviolet-curable resins and oxygen-curable resins; colorants such as pigments and dyes; antioxidants, ultraviolet absorbers, and light stabilization. Additives such as agents, flame retardants and the like may optionally be used.

[0082]

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

In the following Examples and Comparative Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

In the following examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)”
Is a gel permeation chromatography (GP
Calculated by standard polystyrene conversion method using C).
However, a GPC column packed with a polystyrene crosslinked gel and chloroform as a GPC solvent were used. (Production Example 1) In a 10 L separable flask equipped with a reflux tube and a stirrer, CuBr (42.0 g, 0.293 m
ol), and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (559 mL) was added, and the mixture was placed in an oil bath at 70 ° C. for 4 hours.
Stir for 5 minutes. Add butyl acrylate (1.00k
g) Diethyl 2,5-dibromoadipate (176)
g, 0.488 mol), pentamethyldiethylenetriamine (4.00 mL, 3.32 g, 19.2 mmol)
l) (hereinafter triamine) was added and the reaction was started. With heating and stirring at 70 ° C., butyl acrylate (4.00 kg) was continuously added dropwise over 190 minutes.
During the dropping of butyl acrylate, triamine (4.00 m
L, 3.32 g, 0.0192 mol). 310 minutes after the start of the reaction, 1,7-octadiene (1.44 L, 1.07 kg, 9.75 mol), triamine (20.5 mL, 17.0 g, 98.1 mol)
Was added and the mixture was heated and stirred at 70 ° C. for 210 minutes.

After diluting the reaction mixture with hexane and passing through an activated alumina column, volatile components were distilled off under reduced pressure to obtain an alkenyl group-terminated polymer (polymer [1]). The number average molecular weight of the polymer [1] was 14,000, and the molecular weight distribution was 1.3.

In a 10 L separable flask equipped with a reflux tube, polymer [1] (2.7 kg) and potassium benzoate (142) were added.
g) and N, N-dimethylacetamide (2.7 L) were charged and heated and stirred at 70 ° C. for 25 hours under a nitrogen stream. After removing N, N-dimethylacetic acid amide under reduced pressure by heating, the mixture was diluted with toluene. Solids insoluble in toluene (KBr and excess potassium benzoate were filtered through an activated alumina column. The volatiles in the filtrate were distilled off under reduced pressure to obtain a polymer [2].

In a 2 L round-bottom flask equipped with a reflux tube, polymer [2] (2.7 kg), aluminum silicate (540 g, Kyowa Chemical Co., Ltd., 700 PEL), and toluene (2.7) were added.
L), and the mixture was heated and stirred at 100 ° C. for 5 hours under a nitrogen stream. After the aluminum silicate was removed by filtration, the toluene in the filtrate was distilled off under reduced pressure to obtain a polymer [3].

The polymer [3] (760) was placed in a 1 L pressure-resistant reaction vessel.
g), dimethoxymethylhydrosilane (46.3 mL,
0.38 mol), methyl orthoformate (13.7 mL,
0.13 mmol), and 1,1,3,3 of zero-valent platinum
-Tetramethyl-1,3-divinyldisiloxane complex was charged. However, the amount of the platinum catalyst used was 10 ^-3 equivalent in molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 C for 1 hour. The volatile component of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (polymer [4]). The number average molecular weight of the obtained polymer is GP
C measurement (in terms of polystyrene) revealed a molecular weight distribution of 15,000 and a molecular weight distribution of 1.4. The average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis to be 2.0. (Production Example 2) A 2 L separable flask equipped with a reflux tube and a stirrer was charged with CuBr (22.4 g, 0.156 mol).
l) was charged, and the inside of the reaction vessel was replaced with nitrogen. Add acetonitrile (112 mL) and place in an oil bath at 70 ° C for 30 minutes.
Stirred for minutes. Add butyl acrylate (0.20k
g), methyl 2-bromopropionate (86.9 g,
0.520 mol), pentamethyldiethylenetriamine (0.19 mL, 0.18 g, 1.04 mmol)
(Hereinafter triamine) was added to initiate the reaction. With heating and stirring at 70 ° C., butyl acrylate (0.80 kg) was continuously added dropwise over 150 minutes.
During the dropping of butyl acrylate, triamine (1.81 m
L, 1.71 g, 9.88 mmol). Subsequently, the mixture was heated and stirred at 70 ° C. for 230 minutes.

After diluting the reaction mixture with toluene and passing through an activated alumina column, volatile components were distilled off under reduced pressure to obtain an alkenyl group-terminated polymer (polymer [5]).

In a 2 L separable flask equipped with a reflux tube, polymer [5] (0.937 kg) and potassium acetate (73.5) were added.
g) and N, N-dimethylacetic acid amide (0.8 L) were charged and heated and stirred at 70 ° C. for 5 hours under a nitrogen stream. After removing N, N-dimethylacetic acid amide under reduced pressure by heating, the mixture was diluted with toluene. Solids insoluble in toluene (KBr and excess potassium benzoate were filtered through an activated alumina column. The volatiles in the filtrate were distilled off under reduced pressure to obtain a polymer [6].

In a 2 L round bottom flask equipped with a reflux tube, polymer [6] (0.9 kg), aluminum silicate (180 g, Kyowa Chemical Co., Ltd., 700 PEL), and toluene (0.9 kg) were added.
L), and the mixture was heated and stirred at 100 ° C. for 5 hours under a nitrogen stream. After the aluminum silicate was removed by filtration, the filtrate [toluene] was distilled off under reduced pressure to obtain a polymer [7].

The polymer [7] (760) was placed in a 1 L pressure-resistant reaction vessel.
g), dimethoxymethylhydrosilane (46.3 mL,
0.38 mol), methyl orthoformate (13.7 mL,
0.13 mmol), and 1,1,3,3 of zero-valent platinum
-Tetramethyl-1,3-divinyldisiloxane complex was charged. However, the amount of the platinum catalyst used was 10 ^-3 equivalent in molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 C for 1 hour. The volatile component of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (polymer [8]). The number average molecular weight of the obtained polymer is GP
C measurement (in terms of polystyrene) showed 2,600, and molecular weight distribution was 1.2. The average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis to be 2.0.

100 parts of this polymer [8] was added to N-
(Β-aminoethyl) -γ-aminopropyltrimethoxysilane 3 parts, toluene 5 parts, dibutyltin phthalate 2
Was added to obtain Primer I. (Production Example 3) In toluene (30 g) heated to 110 ° C., butyl acrylate (5.9 g), methyl methacrylate (66 g), stearyl methacrylate (13.2 g),
To a mixture of γ-methacryloxypropylmethyldimethoxysilane (5.4 g), γ-mercaptopropylmethyldimethoxysilane (7.2 g) and toluene (36 g), azobisisobutyronitrile (3
g) was added dropwise over 6 hours, and then 2
A polymerization reaction was carried out for a period of time, and the number average molecular weight (Mn) by GPC (polystyrene conversion) was 2,2 at a solid content of 60%.
00 [9] was obtained.

To 100 parts of the copolymer [9], 2 parts of dibutyltin phthalate was added to obtain a primer II. Example 1 Primer I obtained in Production Example 2 was applied to a glass adherend having a joint width of 10 mm with a brush and cured, and then 100 parts of the polymer [4] obtained in Production Example 1 was added to 100 parts of dibutyltin diacetyl. One part of acetonate was added, mixed and filled. Table 1 shows the evaluation results. In Table 1, the evaluation results of the adhesiveness (destruction state) after curing and curing are as follows: O when the adhesiveness is good and the destruction state is close to cohesion failure, and the adhesion is too poor. The case where it was not good and the failure state was close to adhesion failure was represented by a triangle. Comparative Example 1 The primer II obtained in Production Example 3 was applied and cured in the same manner as in Example 1, and then filled in the same manner as in Example 1. Table 1 shows the evaluation results.

[0095]

[Table 1] From the examples, it can be seen that the primer composition of the present invention can reduce the amount of solvent used, and is particularly suitable as a primer for a vinyl polymer having a crosslinkable silyl group, or a cured product obtained from the composition. I understand.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 133/00 C09D 133/00 C09J 133/00 C09J 133/00 (72) Inventor Kenichi Kitano Kobe, Hyogo Prefecture 1-280 Yoshida-cho, Hyogo-ku Kanebuchi Chemical Industry Co., Ltd. Functional Materials RD Center Kobe Research Laboratory (72) Inventor Yoshiki Nakagawa 1-2-80 Yoshida-cho, Hyogo-ku, Kobe City, Hyogo Prefecture Kanefuchi Chemical Industry Co., Ltd. Functional Materials RD Center Kobe Laboratory

Claims (10)

[Claims] 1. A primer composition comprising 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 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 SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′s may be the same or different) It represents a triorganosiloxy group, and 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,
When two or more Ys are present, they may be the same or different. a is 0, 1, 2, or 3
And b represents 0, 1, or 2. m is 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied. ｝ 2. The primer composition according to claim 1, wherein the ratio of the weight average molecular weight to the number average molecular weight of the vinyl polymer measured by gel permeation chromatography is less than 1.8. 3. The primer composition according to claim 1, wherein the vinyl polymer is a (meth) acrylic polymer. 4. The primer composition according to claim 1, wherein the method for producing the vinyl polymer is a living radical polymerization method. 5. The method according to claim 1, wherein the vinyl polymer is produced 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. The primer composition according to any one of the above. 6. The primer composition according to claim 1, which has at least one crosslinkable silyl group represented by the general formula (1) at a molecular chain terminal. 7. A vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1) comprising the following steps: (1) an organic halide or a sulfonyl halide compound as an initiator, a transition metal complex To produce a vinyl polymer having a halogen terminal at the terminal by radical polymerization of a vinyl monomer using as a catalyst, and (2) reacting an oxyanion having an alkenyl group to replace the halogen, thereby forming an alkenyl group at the terminal. 7. A polymer obtained by producing a vinyl-based polymer having the same, and reacting with (3) a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1). 3. The primer composition according to item 1. 8. A vinyl polymer having a crosslinkable silyl group represented by the general formula (1) is obtained by the following steps: (1) a vinyl monomer is polymerized by a living radical polymerization method to form the vinyl polymer. Manufacturing,
(2) Subsequently, at least two alkenyl groups having low polymerizability
A vinyl polymer having a terminal alkenyl group is produced by reacting a compound having two or more compounds, and the terminal alkenyl group is converted into a silyl group-containing substituent for reacting a hydrosilane compound having a crosslinkable silyl group represented by the general formula 1. ;
The primer composition according to any one of claims 1 to 6, which is a polymer obtained by: 9. The primer composition according to claim 1, further comprising a curing catalyst. 10. A compound having an organic group having at least one of nitrogen, oxygen and sulfur atoms and a compound having a crosslinkable silyl group in one molecule as an adhesion promoter.
10. The composition according to any one of 9 above.