JP2000143853A - Foamable resin composition and foam prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which gives a foam excellent in resistances to weather and heat, paintability and adhesiveness by incorporating a vinyl polymer having a crosslinking silyl group and a blowing agent into the same. SOLUTION: This composition contains a vinyl polymer having at least one crosslinking silyl group of the formula: -[Si(R1)2-b(Y)bO]m-Si(R2)3-a(Y)a and preferably having a mol.wt. distribution lower than 1.8 and a blowing agent. In the formula, R1 and R2 are each 1-20C alkyl, 6-20C aryl, 7-20C aralkyl, or a triorganosiloxy group of the formula: (R')3SiO- (wherein R' is a 1-20C monovalent hydrocarbon group; Y is OH or a hydrolyzable group; a is 1-3; b is 0-2; and m is 0-19 provided a+mb is 1 or higher). Preferably, the vinyl polymer is a (meth)acrylic polymer, is produced by living radical polymerization and/or atom transfer radical polymerization, and has at least one crosslinking silyl group of the formula at the molecular ends.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a foamable resin composition and a foam obtained by foaming and curing the composition. More specifically, a vinyl polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group (hereinafter, also referred to as a crosslinkable silyl group) capable of being crosslinked by forming a siloxane bond. The present invention relates to a foamable resin composition containing the resin composition and a foaming agent, and a foam obtained by foaming and curing the resin composition.

[0002]

2. Description of the Related Art Conventionally, as a foam of a polymer compound,
Polystyrene, polyethylene, polypropylene, polyvinyl chloride, etc. are used as bead foams or foam sheets and boards, making use of their properties of heat insulation, light weight, cushioning, etc. in the civil engineering and construction field, packaging field, home appliance field, automobile field, etc. It's being used. However, all of these require a large facility for foam molding and have a problem that so-called in-situ foaming cannot be performed.

On the other hand, in a method of obtaining a foam by in-situ foaming such as injection or spraying, as compared with a so-called regular foam, the foam is amorphous and can be filled without gaps. When used in the field of civil engineering and construction, etc., there are advantages such as improvement of heat insulation properties, shortening of construction period, and low transportation cost. Representative examples of such foams include urethane foam and silicone foam.

However, in the case of urethane foam, there is a concern that the toxicity of isocyanate which is one of the main raw materials is concerned, and furthermore, the obtained foam is not high in weather resistance and cannot be used particularly in outdoor exposed parts. There is. Also, in the case of silicone foam, although there is no problem with weather resistance, it is impossible to apply paint, especially water-based paint, which has recently become widely used, so use wallpaper and siding boards and adhesives. There is a problem such as not being able to adhere even if it tries to adhere.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide a foamable resin composition capable of providing a foam having excellent weather resistance, heat resistance, paintability and adhesion. It is the purpose.

[0006]

Means for Solving the Problems The following two components: (A) a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1), and-[Si (R ¹ ) _{2 -b} (Y) _b O] _m -Si (R ² ) _3-a (Y) _a (1) wherein R ¹ and R ² are the same or different and each have 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
Represents a triorganosiloxy group represented by SiO— (wherein, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms).
A plurality of R's 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. When two or more Y are present, they may be the same or different. a represents 0, 1, 2 or 3. b represents 0, 1, or 2. m shows the integer of 0-19.
However, it satisfies that a + mb ≧ 1. It has been found that the above problem can be solved by using a foamable resin composition containing (B) a foaming agent and foaming and curing the foamable resin composition, and arrived at the present invention.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The foamable resin composition of the present invention comprises the above-mentioned vinyl polymer (A) and a foaming agent (B). Hereinafter, the foamable resin composition of the present invention will be described in detail.

[About the vinyl polymer of the component (A)]
The vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1), which is the component (A), crosslinks by forming a siloxane bond.
In the above general formula (1), R ¹ and R ² are the same or different and are 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 ') shows a triorganosiloxy group represented by ₃ SiO-. R 'represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. A plurality of R's may be the same or different. When two or more R ¹ or R ² are present, they may be the same or different. In the general formula (1), Y represents a hydroxyl group or a hydrolyzable group. When there are two or more Y,
They may be the same or different. Y
Is preferably in the range of 1 to 5.

The hydrolyzable group is not particularly restricted but includes, for example, hydrogen, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group,
Examples include an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group is preferable because it has a mild hydrolytic property and is easy to handle.

In the general formula (1), a is 0, 1,
Represents 2 or 3, b represents 0, 1 or 2, and m represents an integer. Y can be bonded to one silicon atom in the range of 1-3. a, b and m are a + mb ≧ 1
To be satisfied. That is, the general formula (1) contains at least one Y.

One or more silicon atoms constituting the above-mentioned crosslinkable silyl group may be present. In the case of silicon atoms connected by a siloxane bond, m may be from 0 to 19, since it may be up to about 20 atoms.
It is preferred that

The monomers constituting the main chain of the vinyl polymer having at least one crosslinkable silyl group include:
It is not particularly limited as long as it is a vinyl monomer, for example,
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Isobutyl acrylate,
-Tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) -N-octyl acrylate, 2-ethylhexyl (meth) acrylate,
Nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid-2- Methoxyethyl, 3-methoxypropyl (meth) acrylate,
2-hydroxyethyl (meth) acrylate, (meth)
2-hydroxypropyl acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid Ethylene oxide adduct, trifluoromethylmethyl (meth) acrylate, (meth) acrylic acid
2-trifluoromethylethyl, (meth) acrylic acid-
2-perfluoroethylethyl, (meth) acrylic acid-
2-perfluoroethyl-2-perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate,
Perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2- (perfluoromethylmethyl) acrylate, 2-perfluorohexyl (meth) acrylate (Meth) acrylic monomers such as ethyl, 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate; styrene, vinyltoluene, α-methylstyrene, chlorostyrene Styrene monomers such as styrene, styrenesulfonic 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 Acid, maleic acid, Monoalkyl esters and dialkyl esters of formic acid; fumaric acid, monoalkyl esters 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,
Examples thereof include vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or 2
More than one species may be used in combination. In the above expression format, for example, (meth) acrylic acid indicates acrylic acid and / or methacrylic acid.

The vinyl polymer having at least one crosslinkable silyl group is obtained by synthesizing at least 40% by weight of a (meth) acrylic acid monomer among the above monomers from the viewpoint of physical properties ( (Meth) acrylic polymers are preferred. Further, an acrylic polymer obtained by synthesizing the above monomer with an acrylic acid monomer in an amount of 30% by weight or more is more preferable.

The 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.
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 ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn)
Is not particularly limited. However, it is preferable that the molecular weight distribution is narrow in order to suppress the viscosity of the foamable resin composition to a low level, to facilitate handling, and to obtain sufficient cured physical properties. The value of the molecular weight distribution is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, further preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1. 3 or less. Most commonly, the molecular weight distribution is measured by gel permeation chromatography (GPC). Chloroform or THF is used as the mobile phase, and a polystyrene gel column is used as the column, and the number average molecular weight and the like can be determined by values 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 versatility and controllability of monomers, a method in which a crosslinkable silyl group is directly introduced into a main chain by a radical polymerization method, and a method in which a crosslinkable silyl group can be converted into a crosslinkable silyl group by one or several steps of reaction. After obtaining a vinyl polymer having the above functional group by a radical polymerization method, it is preferable to convert this specific functional group into a crosslinkable silyl group.

In a radical polymerization method used in a method for synthesizing a vinyl polymer having a specific functional group containing a crosslinkable silyl group, a specific functional group is used by using an azo compound, a peroxide or the like as a polymerization initiator. "General radical polymerization method" that simply copolymerizes a monomer having a group and a vinyl monomer, and "Controlled radical polymerization method" that can introduce a specific functional group at a controlled position such as a terminal. Can be classified.

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 an attempt is made to obtain a polymer having a high functionalization rate, it is necessary to use this monomer in a considerably large amount, 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. Also, because it is a 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 polymerization is carried out using a chain transfer agent having a specific functional group to obtain a vinyl polymer having a functional group at a terminal. It can be classified as a “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing a polymer growth terminal without causing a termination reaction or the like.

The "chain transfer agent method" can obtain a polymer having a higher functionalization rate as compared with the "general radical polymerization method" and can be used in the present invention. Therefore, a considerably large amount of a chain transfer agent having a specific functional group is required, and there is an economical problem including processing. Also,
Similar to the above-mentioned "general radical polymerization method", since it is a free radical polymerization, there is a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization which is difficult to control because the polymerization rate is high and a termination reaction is likely to occur due to coupling between radicals. The reaction hardly occurs and the molecular weight distribution is narrow (Mw / Mn is 1.
(Approximately 1 to 1.5) A polymer can be obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator. Therefore, the `` living radical polymerization method '' has a narrow molecular weight distribution and can obtain a polymer having a low viscosity, and can introduce a monomer having a specific functional group into almost any position of the polymer, It is more preferable as a method for producing the vinyl polymer having the specific functional group. In the narrow sense, living polymerization refers to polymerization in which a terminal always has activity and a molecular chain grows. Pseudo-living polymerization that grows while in equilibrium is also included. 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. In recent years, various groups have been actively studying this "living radical polymerization method", and examples include:
For example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994.
Year, Vol. 116, p. 7943, using a cobalt porphyrin complex, Macromolecules, 1994, 27.
Vol., P. 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 Radic)
al Polymerization: ATRP). Among the "living radical polymerization method",
"Atom transfer radical polymerization", 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, is characterized by a functional group It is more preferable as a method for producing a vinyl polymer having a specific functional group, since it has a halogen or the like which is relatively advantageous for the conversion reaction at the terminal and has a large degree of freedom in designing an initiator and a catalyst. As this atom transfer radical polymerization method, for example, Ma
tyjaszewski et al., Journal of American Chemical Society (J. Am. Chem. S.
oc. , 1995, 117, 5614, Macromolecules, 1
995, 28, 7901, Science
nce), 1996, 272, 866, WO96.
/ 30421, WO97 / 18247 or Sawamoto et al., Macromolecules (Ma
cromolecules), 1995, volume 28, 1
721 pages.

Examples of the initiator in the "atom transfer radical polymerization method" include organic halides, especially organic halides having a highly reactive carbon-halogen bond, and sulfonyl halide compounds. Examples of the organic halide having a carbon-halogen bond having a particularly high reactivity include a carbonyl compound having a halogen at the α-position and a compound having a halogen at the benzyl position. These may be used alone or in combination of two or more. The transition metal complex used as a catalyst in the above “atom transfer radical polymerization method” is not particularly limited.
Complexes having a Group 10 element, a Group 11 element or a Group 11 element as a central metal can be used. Preferred are 0-valent copper, 1
Complexes of divalent copper, divalent ruthenium, divalent iron or divalent nickel can be mentioned. Among them, 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 restricted but includes, for example, cuprous chloride, cuprous bromide, cuprous iodide,
Cuprous cyanide, cuprous oxide, cuprous perchlorate and the like can be mentioned. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,2
A ligand such as 10-phenanthroline and a derivative thereof, a polyamine such as tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltris (2-aminoethyl) amine is added.

Also, tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ )
Are also suitable as catalysts. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator. Furthermore, a bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ) and a bis (triphenylphosphine) complex of divalent nickel (NiC
l ₂ (PPh ₃ ) ₂ ) and a bistributylphosphine complex of divalent nickel (NiBr ₂ (PBu ₃ ) ₂ )
Are also suitable as catalysts.

The above polymerization reaction can be carried out without a solvent or in various solvents. The solvent is not particularly limited and includes, for example, hydrocarbon solvents such as benzene and toluene;
Ether solvents such as diethyl ether and 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, tert Alcohol solvents such as -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 may be used alone or in combination of two or more.

The above "atom transfer radical polymerization method"
It can be performed in the range of 0 to 200 ° C. Preferably,
The range is from room temperature to 150 ° C.

Next, a method for producing a vinyl polymer having at least one crosslinkable silyl group represented by the above general formula (1) is specifically exemplified in the following methods [A] to [E]. It will be described, but not limited thereto. [A] A method in which a hydrosilane compound having a crosslinkable silyl group is added to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst. [B] A method in which a vinyl polymer having at least one hydroxyl group is reacted 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 synthesizing a vinyl polymer by radical polymerization. [D] A method of radically polymerizing a vinyl monomer using a chain transfer agent having a crosslinkable silyl group. [E] at least one highly reactive carbon-halogen bond
A method of reacting a stable carbanion having a crosslinkable silyl group with a vinyl polymer having two or more vinyl polymers.

The method for synthesizing the vinyl polymer having at least one alkenyl group used in the above synthesis method [A] is not particularly limited.
a) to [Aj]. [A-a] When synthesizing a vinyl polymer by radical polymerization, it has both a predetermined vinyl monomer and a polymerizable alkenyl group represented by the following general formula (2) or the like and a low polymerizable alkenyl group. 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) ( wherein, R ³ is .R ⁴ represents a hydrogen or a methyl group is -C
(O) O-, or o-, m- or p-phenylene group. R ⁵ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds. R ⁶ 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. The timing of reacting the compound having both the polymerizable alkenyl group and the low polymerizable alkenyl group is not particularly limited. However, in the case where a rubbery property is expected in the obtained cross-linked product, living radical polymerization may be used. It is preferable to react as a second monomer at the end of the polymerization reaction or after the reaction of a predetermined vinyl monomer.

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

The following methods [Ac] to [Af] are as follows:
Has at least one highly reactive carbon-halogen bond
At least the alkenyl group from the vinyl polymer
This is a method for obtaining a vinyl polymer having one. In addition, above
Has at least one highly reactive carbon-halogen bond
Polymer to be described later of [Ea] and [Eb]
It can be obtained by a method. [Ac] Reduce the number of highly reactive carbon-halogen bonds
Allyl tributyl tin to a vinyl polymer having one
Alke such as organotin such as allyltrioctyltin
Reacting an organometallic compound containing
Is substituted with an alkenyl group-containing substituent. [Ad] Reduce the number of highly reactive carbon-halogen bonds
With the following general formula (3) or the like
The stabilized carbanion having an alkenyl group represented by
And substituting the halogen with an alkenyl group. M⁺ C^- (R⁷ ) (R⁸ ) -R⁹ -C (R⁶ ) = CH_Two (3) (where R⁶ Is the same as described above. R⁷ and
R⁸ Are both Carbanion C^- Stabilizes electron suction
Group, or one is the above electron withdrawing group and the other is hydrogen or charcoal.
It represents an alkyl group or a phenyl group having a prime number of 1 to 10.
R⁹ Contains a direct bond or one or more ether bonds
And a divalent organic group having 1 to 10 carbon atoms which may be present. M
⁺ Is an alkali metal ion or a quaternary ammonium ion
To indicate R ⁷ And R⁸ As an electron withdrawing group of
O_Two R, -C (O) R and -CN are preferred. here
R is hydrogen, an alkyl group having 1 to 10 carbon atoms, and 6 to 1 carbon atoms.
0 aryl group or aralkyl group having 7 to 10 carbon atoms
Show. )

[A-e] An enolate anion 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 is added to halogen or acetyl. A method of reacting an alkenyl group-containing electrophilic compound such as an alkenyl group-containing compound having a leaving group such as a group, an alkenyl group-containing carbonyl compound, an alkenyl group-containing isocyanate compound, and an alkenyl group-containing acid halide. [Af] An alkenyl group-containing oxyanion represented by the following general formula (4) or a alkenyl group-containing oxyanion represented by the following general formula (5) is added to a vinyl polymer having at least one highly reactive carbon-halogen bond. Reacting the alkenyl group-containing carboxylate anion to be substituted with the alkenyl group-containing substituent. ^{_{H 2 C = C (R 6}} ) -R 10 -O - M + (4) ( wherein, R ⁶ and M ⁺ are the same as those described above.
R ¹⁰ represents a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds. _{) 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. [A-g] ~
The method of [Aj] can be exemplified. The vinyl polymer having at least one hydroxyl group can be obtained by the following methods [Ba] to [Bi]. [Ag] A method in which a vinyl polymer having at least one hydroxyl group is allowed to act on a base such as sodium hydroxide or sodium methoxide 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 of reacting a vinyl polymer having at least one hydroxyl group 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, the above-mentioned [A-
When a halogen atom is not directly involved in introducing an alkenyl group, such as the methods a) and [Ab], it is preferable to use a living radical polymerization method. In this case, the method of [Ab] is more preferable because the control is easier. Among living radical polymerization methods, an atom transfer radical polymerization method is more preferable.

On the other hand, an alkenyl group is converted by converting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond as in the above-mentioned methods [Ac] to [Af]. In the case of introduction, a highly reactive carbon-halogen bond at the end obtained by radical polymerization (atom transfer radical polymerization) using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is used. It is preferable to use a vinyl polymer having at least one polymer. The method of [A-f] is more preferable because the control is easier.

In the above synthesis method [A],
The hydrosilane compound having a crosslinkable silyl group is not particularly limited, and examples thereof include a compound represented by the following 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 is the same as described above.) Among them, a compound represented by the following general formula (7) is preferably used because it is easily available. H-Si (R ² ) _3-a (Y) _a (7) (wherein R ² , Y and a are the same as described above)

In the above synthesis method [A], when the hydrosilane compound having a 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, and includes, for example, a substance in which platinum solid is dispersed in a carrier such as platinum alone, alumina, silica, and carbon black; chloroplatinic acid; chloroplatinic acid and alcohol;
Complexes with aldehydes, ketones, etc .; platinum-olefin complexes, platinum (0) -divinyltetramethyldisiloxane complexes; RhCl (PPh ₃ ) ₃ , RhCl ₃ , RuCl
₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂
· H ₂ O, can be cited NiCl _2, TiCl ₄ compounds other than platinum compounds such like. These may be used alone or in combination of two or more.

The method for synthesizing the vinyl polymer having at least one hydroxyl group, which is used in the above-mentioned synthesis method [B] and further in the above-mentioned methods [Ag] to [Aj], is not particularly limited. For example, the following [Ba]
To [B-i]. [Ba] When a vinyl polymer is synthesized by radical polymerization, a compound having both a polymerizable alkenyl group and a hydroxyl group represented by the following general formula (8) and the like are reacted together with a predetermined vinyl monomer. Method. H ₂ C ＝ C (R ³ ) —R ⁴ —R ⁵ —OH (8) (In the formula, R ³ , R ⁴ and R ⁵ are the same as those described above.) The above polymerizable alkenyl group The timing of reacting the compound having both a hydroxyl group and a hydroxyl group is not particularly limited, but when a rubbery property is expected in the obtained crosslinked product, the living radical polymerization is terminated at the end of the polymerization reaction or the reaction of a predetermined vinyl monomer is terminated. It is preferred to react later as a second monomer. [Bb] In the synthesis of a vinyl polymer by living radical polymerization, for example, 10-undecenol, 5-
A method of reacting alkenyl alcohols such as hexenol and allyl alcohol. [Bc] A method of radically polymerizing the above-mentioned vinyl monomer 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] JP-A-6-239912, JP-A-8-19912
A method of radically polymerizing the above-mentioned vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator by a method disclosed in Japanese Patent No. 283310 or the like. [Be] A method disclosed in Japanese Patent Application Laid-Open No. 6-116312 or the like, in which a vinyl monomer is radically polymerized using an excess of alcohols. [Bf] By the method disclosed in JP-A-4-132706 or the like, a 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 introducing a hydroxyl group into the terminal. [Bg] A vinyl-based 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) or the like to convert the halogen. A method of substituting with a hydroxyl group-containing substituent. ^{M + C - (R 7)} (R 8) -R 9 -OH (9) ( wherein, an electron withdrawing group of R ^7, R ⁸ and R ⁹ are the same as those described above .R ⁷ and R ⁸ As -CO ₂
R, -C (O) R and -CN are preferred. Here, R is the same as described above. [Bh] An enolate anion 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 aldehyde or a ketone How to react the kind. [Bi] A vinyl-based polymer having at least one highly reactive carbon-halogen bond, a hydroxyl-containing oxyanion represented by the following general formula (10) or a oxyanion represented by the following general formula (11) 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 those described ^{above.) HO-R 11 -C (} O) O - M + (11) ( in the formula , R ¹¹ and M ⁺ are the same as described above.)

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

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

In the above synthesis method [B],
The compound having both a functional group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group is not particularly limited. For example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyl Triethoxysilane and the like can be mentioned. These may be used alone or in combination of two or more.

In the reaction in the above-mentioned synthesis method [B], a known urethanization catalyst can be used if necessary.

The compound having both a polymerizable alkenyl group and a crosslinkable silyl group used in the above synthesis method [C] is not particularly limited. For example, trimethoxysilylpropyl (meth) acrylate, methyldimethoxysilylpropyl (meth) acrylate And the like represented by the following general formula (12). ^{_{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) ( Formula Where R ¹ , R ² , R ³ , R ⁴ , Y, a, b and m
Is the same as described above. R ¹² represents a direct bond or one carbon atom which may contain one or more ether bonds.
And represents a divalent organic group of -20. These may be used alone or in combination of two or more. )

In the above-mentioned synthesis method [C], the timing of reacting the compound having both the polymerizable alkenyl group and the crosslinkable silyl group is not particularly limited, but when the obtained cross-linked product is expected to have rubber-like properties, In the living radical polymerization, it is preferable to react as a second monomer at the end of the polymerization reaction or after completion of the reaction of a predetermined vinyl monomer.

In the above synthesis method [D],
The chain transfer agent having a crosslinkable silyl group is not particularly limited.
Examples thereof include mercaptans having a crosslinkable silyl group and hydrosilanes having a crosslinkable silyl group, as disclosed in Japanese Patent No. 55444. Further, 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 above synthesis method [E], further, the above methods [Ac] to [Af] and [Bf] to [B-
The method for synthesizing the vinyl polymer having at least one highly reactive carbon-halogen bond, which is also used in i), is not particularly limited, and for example, the following [Ea]
And [Eb]. [Ea] In a method disclosed in Japanese Patent Application Laid-Open No. 4-132706, radical polymerization is performed using a halide such as carbon tetrachloride, ethylene chloride, carbon tetrabromide, or methylene bromide as a chain transfer agent. Method (chain transfer agent method). [Eb] Atom transfer radical polymerization using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst.

In the above synthesis method [E],
The stabilized carbanion having a crosslinkable silyl group is not particularly limited, and examples thereof include a compound represented by the following general formula (13). ^{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
Is the same as described above. R ¹³ represents a direct bond or a carbon atom which may contain one or more ether bonds.
And represents a divalent organic group of -20. 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 group having 7 to 10 carbon atoms. The electron-withdrawing groups for R ⁷ and R ⁸ include —CO ₂ R, —C (O)
R and -CN are preferred. Here, R is the same as described above. )

When rubber-like properties are particularly required for a foam obtained by foaming and curing the foamable resin composition of the present invention, the molecular weight between cross-linking points which greatly affects rubber elasticity can be increased. Preferably, at least one of the crosslinkable silyl groups is at the end of the molecular chain. More preferably, all the crosslinkable silyl groups have at the terminal of the molecular chain.

A method for producing a vinyl polymer having at least one crosslinkable silyl group at a molecular terminal, in particular, a (meth) acrylic polymer is disclosed in JP-B-3-14068 and JP-B-4-55444. JP-A-6-2119
No. 22, for example. However, since these methods are free radical polymerization methods using the above “chain transfer agent method”, the resulting polymer has a relatively high proportion of crosslinkable silyl groups at the molecular chain terminals, while having Mw / M
The value of the molecular weight distribution represented by n is generally as large as 2 or more,
There is a problem that the viscosity increases. Therefore, in order to obtain a vinyl polymer having a narrow molecular weight distribution and a low viscosity and having a high proportion of a crosslinkable silyl group at a molecular chain end, the above-mentioned "living radical polymerization method" is used. Is preferred. Therefore, the vinyl polymer having at least one hydroxyl group, halogen or alkenyl group used for synthesizing the vinyl polymer having at least one crosslinkable silyl group has these functional groups at the molecular chain terminals. Are preferred.

In order to obtain a vinyl polymer having at least one crosslinkable silyl group at the molecular chain terminal by using the more preferred “atom transfer radical polymerization method” among the above “living radical polymerization methods”, As the agent, it is preferable to use an organic halide or a sulfonyl halide compound having two or more starting points. The resulting vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal of the molecular chain can be obtained by the above-described method using at least one crosslinkable silyl group at the terminal of the molecular chain.
It can be easily changed to a vinyl polymer having one.

Organic Halogen Having Two or More Starting Points
Especially as a halide or a sulfonyl halide compound
Without limitation, for example, the following compounds can be mentioned.
You. Specific examples thereof include o-, m-, p-XCH_Two -C₆ H_Four -CH_Two X, o
-, M-, p-CH_Three C (H) (X) -C₆ H_Four -C
(H) (X) CH_Three , O-, m-, p- (CH_Three )_TwoC
(X) -C₆ H_Four -C (X) (CH_Three )_Two (However, in the above formula, C₆ H_Four Represents a phenylene group.
X represents chlorine, bromine, or iodine) RO_Two CC (H) (X)-(CH_Two )_n -C (H)
(X) -CO_Two R, RO_TwoCC (CH_Three ) (X)-
(CH_Two )_n -C (CH_Three ) (X) -CO_Two R, RC
(O) -C (H) (X)-(CH_Two )_n -C (H)
(X) -C (O) R, RC (O) -C (CH_Three ) (X)
− (CH_Two )_n -C (CH_Three ) (X) —C (O) R (wherein R is an alkyl group having 1 to 20 carbon atoms, aryl)
Or an aralkyl group. n is an integer from 0 to 20
X represents chlorine, bromine or iodine.) XCH_Two -C (O) -CH_Two X, H_Three CC (H)
(X) -C (O) -C (H) (X) -CH_Three , (H_Three 
C)_Two C (X) -C (O) -C (X) (CH_Three )_Two , C
₆ H_Five C (H) (X)-(CH_Two )_n -C (H) (X)
C₆ H_Five (In the above formula, X represents chlorine, bromine or iodine, and n is
XCH represents an integer of 0 to 20) XCH_Two CO_Two − (CH_Two )_n -OCOCH_Two X, CH
_Three C (H) (X) CO_Two− (CH_Two )_n -OCOC
(H) (X) CH_Three , (CH_Three )_Two C (X) CO_Two −
(CH_Two )_n -OCOC (X) (CH_Three )_Two (Wherein, n represents an integer of 1 to 20) XCH_Two C (O) C (O) CH_Two X, CH_ThreeC (H)
(X) C (O) C (O) C (H) (X) CH3, (CH
_Three )_Two C (X) C (O) C (O) C (X) (CH_Three)
_Two , O-, m-, p-XCH_Two CO_Two -C₆ H_Four -OC
OCH_Two X, o-, m-, p-CH_Three C (H) (X) C
O_Two -C₆ H_Four -OCOC (H) (X) CH_Three, O-,
m-, p- (CH_Three )_Two C (X) CO_Two -C₆ H_Four -O
COC (X) (CH_Three )_Two , O-, m-, p-XSO_Two 
-C₆ H_Four -SO_Two X (wherein, X represents chlorine, bromine, or iodine). These may be used alone or in combination of two or more.
You may use together.

The compound has a crosslinkable silyl group at both molecular chain terminals.
In order to obtain a vinyl polymer,
Has two starting points as an initiator in the "cal polymerization method"
Organic halide or sulfonyl halide compound
Other than the method using an organic compound having a crosslinkable silyl group.
A method using a logenide is also preferable. The above crosslinkable silyl
The organic halide having a group is not particularly limited,
For example, a compound represented by the following general formula (14) or (15)
And the like. R¹⁵R¹⁶C (X) -R¹⁷-R¹⁸-C (H) (R¹⁹) CH_Two -[Si (R¹ )_2-b (Y)_b O]_m -Si (R^Two )_3-a (Y)_a (14) (where R¹ , R^Two , A, b, m, X and Y are as described above.
The same as R ¹⁵And R¹⁶Are the same or different
Hydrogen, an alkyl group having 1 to 20 carbon atoms, 6 to
20 aryl groups or aralkyl groups having 7 to 20 carbon atoms
Is shown. R¹⁵And R ¹⁶Are interconnected at the other end.
You may. R¹⁷Is -C (O) O-, -C (O)-, and
Represents an o-, m-, p-phenylene group. R¹⁸Is directly
May contain a bond or one or more ether bonds
A divalent organic group having 1 to 10 carbon atoms. R¹⁹Is hydrogen,
C1-C10 alkyl group, C6-C10 aryl
And a aralkyl group having 7 to 10 carbon atoms. ) (R^Two )_3-a (Y)_a Si- [OSi (R¹ )_2-b (Y)_b ]_m − CH_Two -C (H) (R¹⁹) -R¹⁸-C (R¹⁵) (X) -R¹⁷-R¹⁶ (15) (where R¹ , R^Two , R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹,
a, b, m, X and Y are the same as those described above.
You. )

When the above-mentioned "atom transfer radical polymerization" is carried out using the above-mentioned organic halide having a crosslinkable silyl group as an initiator, a crosslinkable silyl group is provided at one end and a highly reactive compound is provided at the other end. A vinyl polymer having a carbon-halogen bond is obtained. If the terminal halogen atom of this vinyl polymer is converted into a crosslinkable silyl group-containing substituent using the method described above, a vinyl polymer having a crosslinkable silyl group at both molecular chain terminals can be obtained.

The above-mentioned cross-linking can also be carried out by coupling a halogen atom of the vinyl polymer with a compound having a total of two or more same or different functional groups capable of replacing the above-mentioned terminal halogen atom. A vinyl polymer having a reactive silyl group at both molecular chain terminals can be obtained. The compound having a total of two or more identical or different functional groups capable of replacing the halogen atom at the terminal end is not particularly limited, and examples thereof include polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof;
Examples thereof include alkali metal sulfides.

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 terminal and a halogen atom at the other terminal is obtained. can get. If the terminal halogen atom of this vinyl polymer is converted into an alkenyl-containing substituent using the method described above, a vinyl polymer having alkenyl groups at both molecular chain terminals can be obtained. By converting these alkenyl groups into crosslinkable silyl groups by the above-described method or the like, a vinyl polymer having the crosslinkable silyl groups at both molecular chain terminals can be obtained.
The vinyl polymer having at least one crosslinkable silyl group at the terminal of the molecular chain can be obtained by optionally combining the above-described methods and the like. Typical synthesis steps include the following Synthesis Examples A and B. it can.

[0056]Synthesis process A  (1) Organic halide or sulfonyl halide
Vinyl compounds using compounds, etc. as initiators and transition metal complexes as catalysts
Halogen atom is formed by radical polymerization of monomer.
Step of synthesizing terminal vinyl polymer, (2) before
The terminal having a halogen atom at the terminal obtained in the step (1)
Oxyanion having an alkenyl group and an alkenyl group
Substitution of halogen by reaction
A step of synthesizing a vinyl polymer having a kenyl group, and
And (3) alkenyl at the terminal obtained in the step (2).
General terminal alkenyl groups of vinyl polymers
Hydrosila having a crosslinkable silyl group represented by the formula (1)
Having a crosslinkable silyl group by adding
A synthesis step comprising the step of converting

[0057]Synthesis process B  (1) Vinyl monomer is prepared by living radical polymerization
Process to synthesize a vinyl polymer by polymerization.
Step (2): the vinyl polymer obtained in the step (1) and
Compound having at least two alkenyl groups having low polymerizability
Having an alkenyl group at the end by reacting
(3) synthesizing a vinyl polymer,
Vinyl having a terminal alkenyl group obtained in step (2)
Formula (1) is added to the terminal alkenyl group of
A hydrosilane compound having a crosslinkable silyl group
To convert to a substituent containing a crosslinkable silyl group
Synthesis process consisting of steps.

[About the foaming agent of the component (B)] The foaming agent of the component (B) is a component (A) of a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1). There is no particular limitation as long as it can be foamed during curing. Examples thereof include volatile hydrocarbon compounds such as propane, butane, pentane, and cyclopentane; halogenated hydrocarbon compounds such as chlorofluorocarbon, chlorofluorocarbon, and methylene chloride; air, hydrogen, nitrogen, oxygen, and carbon dioxide. Gases such as carbon are exemplified. When the foaming agent is a volatile hydrocarbon compound or halogenated hydrocarbon compound, the foaming agent is preliminarily mixed with the vinyl polymer as the component (A), and these are vaporized by reducing or heating. When the foaming method utilizing physical properties by causing hydrogen, nitrogen, oxygen, carbon dioxide or the like, for example, a method of adding a silicon hydride compound and a hydroxyl group-containing compound and generating hydrogen by the reaction of both, an azo compound Foaming methods utilizing chemical properties, such as a method of decomposing nitrogen or peroxide to generate nitrogen or oxygen, a method of adding an isocyanate compound and water and generating carbon dioxide by a reaction, and the like. Further, a mechanical foaming method such as a method in which air entrained by mechanical stirring is utilized as a foam, and the like can also be mentioned.

In curing the foamable resin composition of the present invention, a condensation catalyst may be used. Titanate such as tetrabutyl titanate and tetrapropyl titanate; organic solvents such as dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dimethoxide, tin octylate, and tin naphthenate; Tin compounds; lead octylate, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine,
Triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine,
Cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,
4,6-tris (dimethylaminomethyl) phenol,
Amine compounds such as morpholine, N-methylmorpholine, 1,3-diazabicyclo (5,4,6) undecene-7 or carboxylic acid salts thereof; amine compounds such as a reaction product or a mixture of laurylamine and tin octylate Reactants and mixtures of compounds with organotin compounds; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines and epoxy compounds;
Silane coupling agent having an amino group, for example, γ-
One or more known silanol catalysts such as aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane may be used as necessary. When the hydrolyzable group Y is an alkoxy group, a curing catalyst is preferably used because the curing rate is slow only with the vinyl polymer of the component (A).

The foamable resin composition of the present invention contains, in addition to the above condensation catalyst, a filler, a plasticizer, a sagging agent, and the like for the purpose of adjusting various physical properties of the foamable resin composition or foam. A foam stabilizer, a coloring agent, an adhesion promoter, an antioxidant, a flame retardant, a curability regulator, a foaming rate regulator, a weather resistance improver, a mechanical property modifier, and the like can be blended. Reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite Fillers such as organic bentonite, ferric oxide, zinc oxide, activated zinc white and shirasu balloon; fibrous fillers such as asbestos, glass fibers and filaments can be used. If you want to obtain a cured product with high strength with these fillers, mainly fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate,
A filler selected from calcined clay, clay and activated zinc white can be added. When it is desired to obtain a cured product having low strength and large elongation, a filler mainly selected from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. These fillers may be used alone or in combination of two or more.

As the plasticizer, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate and butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, etc. for the purpose of adjusting physical properties and controlling properties. Non-aromatic dibasic acid esters such as diethylene glycol dibenzoate;
Esters of polyalkylene glycols such as triethylene glycol dibenzoate; phosphates such as tricresyl phosphate and tributyl phosphate; paraffin chlorides; and hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl alone. Alternatively, two or more kinds can be used in combination. In addition, these plasticizers can be blended at the time of polymer production.

Polyamide waxes, hydrogenated castor oil derivatives; calcium stearate;
Examples include metal soaps such as aluminum stearate and barium stearate, which can be used as appropriate according to the purpose of use. Various silane coupling agents as physical property modifiers,
For example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldisilane Alkylisopropenoxysilanes such as isopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N- (β
-Aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Alkoxysilanes having a functional group such as mercaptopropylmethyldimethoxysilane; silicone varnishes; and polysiloxanes are added as necessary. By using the physical property adjusting agent, the hardness of the composition of the present invention when it is cured can be increased, or the hardness can be decreased, and elongation can be obtained.

Examples of the adhesion promoter include epoxy resin, phenol resin, sulfur, various silane coupling agents, alkyl titanates, aromatic polyisocyanates, etc., and can improve the adhesion to the adherend.

The foamable resin composition of the present invention and a foam obtained by curing the composition are prepared as a one-component type in which all the components are premixed, sealed and stored, and after application, are cured by moisture in the air. It is also possible to separately mix components such as a curing catalyst, a filler, a plasticizer, and water as a curing agent, and to prepare a two-component type in which the compounded material and the polymer composition are mixed before use. Can also.

As a molding method, various molding methods of urethane foam and silicone foam are possible, and are not limited to the in-situ foaming method. Batch and continuous systems are possible. A so-called slab foaming method, a casting method, an injection molding method, and the like are possible. The molding temperature can be at room temperature, but when equipment can be used, a heating method is preferable for improving productivity.

More specific uses of the foamable resin composition of the present invention and the foam obtained by foaming and curing the composition include heat insulating materials, cushion materials, sound absorbing materials, vibration damping materials, artificial leather, and artificial leather. Examples include a mold material, a molding material, a potting material, and the like.

[0067]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Synthesis Example 1 In a nitrogen atmosphere, ethylene glycol (10.9 mL, 1
95 mmol) and pyridine (3 g, 39 mmol)
2-bromopropionic acid chloride (2 mL, 3.35 g, 19.5 mmol) was added to an HF solution (10 mL) at 0 ° C.
And slowly dripped. The solution was stirred for 2 hours at the same temperature. Dilute hydrochloric acid and ethyl acetate were added to separate two layers, and the organic layer was washed with dilute hydrochloric acid and brine, and dried over Na ₂ SO ₄ . The volatiles were distilled off under reduced pressure to obtain a crude product (3.0
7g). The crude product was distilled under reduced pressure to obtain (70
To 73 ° C., 0.5 mmHg) to obtain hydroxyethyl-2-bromopropionate represented by the following formula (2.14 g,
56%). _{H 3 CC (H) (Br} ) C (O) O (CH 2) 2 -OH

Acrylic acid-n-
Butyl (112 mL, 100 g, 0.78 mol), the hydroxyl-containing initiator obtained above (3.07 g, 15.6 m)
mol), cuprous bromide (2.24 g, 15.6 mmol)
l), 2,2'-bipyridyl (4.87 g, 31.2 m
mol), ethyl acetate (80 mL), and acetonitrile (20 mL), and nitrogen gas was bubbled to remove dissolved oxygen. The mixture was heated to 130 ° C. and reacted for 2 hours. The reaction vessel was returned to room temperature, and 2-hydroxyethyl methacrylate (3.92 mL,
4.06 g, 31.2 mmol) at 110 ° C.
Allowed to react for hours. The mixture was diluted with ethyl acetate (200 mL), and the insolubles were filtered off. The filtrate was washed with 10% hydrochloric acid and brine, and the organic layer was dried over Na ₂ SO ₄ . The solvent was distilled off under reduced pressure to obtain 82 g of poly (n-butyl acrylate) having a hydroxyl group at a terminal. The number average molecular weight of the obtained polymer was 5,100 by GPC measurement (mobile phase chloroform, converted to polystyrene), and the molecular weight distribution was 1.29.
Met.

Next, at the terminal obtained as described above,
Poly (n-butyl acrylate) having a hydroxyl group (50
g) and pyridine (10 mL) in toluene (100
mL) at 75 ° C under nitrogen atmosphere.
Lido (7.22 mL, 6.81 g, 33.6 mmol)
Was slowly added dropwise and stirred at 75 ° C. for 3 hours. Generate
The white solid was filtered and the organic layer was washed with dilute hydrochloric acid and brine.
The organic layer with Na_Two SO_Four And dried. Concentrate under reduced pressure
To obtain poly (acrylic) having alkenyl groups.
(N-butyl acid) (43 g) was obtained. Number average of polymer
GPC measurement (mobile phase chloroform, polystyrene)
(Converted to) and the molecular weight distribution was 1.30.
Was. In addition, the amount of the alkyl introduced per oligomer molecule
The nil group is ¹ According to 1 H-NMR analysis, it was found to be 2.28.
Was.

Next, the poly (butyl acrylate) having an alkenyl group at both terminals obtained above (2 g) and methyldimethoxysilane (0.32) were placed in a 30 mL pressure-resistant reaction vessel.
mL), methyl orthoformate (0.09 mL, 3 equivalents to alkenyl group), 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum (8.3 ×
10 ⁻³ mol / L xylene solution, based on alkenyl group
10 ^-4 equivalents) and stirred at 100 ° C. for 1 hour. The volatiles were distilled off under reduced pressure to obtain 2 g of poly (n-butyl acrylate) having a crosslinkable silyl group. The number average molecular weight of the polymer was measured by GPC (mobile phase chloroform,
According to polystyrene conversion, it was 5,900 and the molecular weight distribution was 1.37. The silyl group introduced per oligomer molecule was found to be 2.24 by ¹ H-NMR analysis.
Was individual.

Synthesis Example 2 A 100 mL glass reaction vessel was charged with butyl acrylate (5
0.0 mL, 44.7 g, 0.349 mol), cuprous bromide (1.25 g, 8.72 mmol), pentamethyldiethylenetriamine (1.82 mL, 1.51 g,
8.72 mmol) and acetonitrile (5 mL)
After cooling, the mixture was degassed under reduced pressure and replaced with nitrogen gas. After stirring well, diethyl 2,5-dibromoadipate (1.57 g, 4.36 mmol) was added and 70
The mixture was heated and stirred at ℃. After 60 minutes, 1,7-octadiene (6.44 mL, 4.80 g, 43.6 mmol) was added, and heating and stirring at 70 ° C. was continued for 2 hours. After treating the mixture with activated alumina, volatiles were distilled off by heating under reduced pressure. The product was dissolved in ethyl acetate and washed with 2% hydrochloric acid and brine. The organic layer was dried over Na ₂ SO ₄ , and volatile components were distilled off by heating under reduced pressure to obtain poly (n-butyl acrylate) having an alkenyl group at the terminal. The number average molecular weight of the obtained polymer was 13100 by GPC measurement (mobile phase chloroform, converted to polystyrene).
And the molecular weight distribution was 1.22. The olefin functional group introduction rate based on the number average molecular weight was 2.01.

A poly (n-butyl acrylate) having an alkenyl group at the terminal (30.5 g) and an aluminum silicate having the same weight as the polymer (Kyowa Chemical: Kyoword 70)
0PEL) was mixed with toluene and stirred at 100 ° C. After 4 hours, the aluminum silicate was filtered, and the volatile matter of the filtrate was distilled off by heating under reduced pressure to purify the polymer.
The above polymer (2) was placed in a 200 mL pressure-resistant glass reaction vessel.
3.3 g), dimethoxymethylhydrosilane (2.55
mL, 20.7 mmol), dimethyl orthoformate (0.
38 mL, 3.45 mmol) and the above platinum catalyst. However, the amount of the platinum catalyst used was 2 × 10 ⁻⁴ equivalent in molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 C for 3 hours. The volatile components of the mixture were distilled off under reduced pressure to obtain poly (n-butyl acrylate) having a silyl group at the terminal. The number of silyl groups introduced per oligomer-1 molecule was 1.41 by ¹ H-NMR analysis.

Synthesis Example 3 In a 50 ml flask, 0.63 g (4.4 mm) of cuprous bromide was placed.
ol), 0.76 g of pentamethyldiethylenetriamine
(4.4 mmol), acetonitrile 5 ml, 2,5-
1.6 g (4.4 mmol) of diethyl dibromoadipate
1) and 44.7 g of butyl acrylate (349 m
mol), and the mixture was frozen and deaerated, and then reacted at 70 ° C. for 7 hours under a nitrogen atmosphere. The copper catalyst was removed and purified through a column of activated alumina to obtain a brominated polymer. The number average molecular weight of the obtained polymer was 10,700 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.15. Under a nitrogen atmosphere, 35 g of a brominated polymer and 2.2 g of potassium pentenoate were placed in a 200 ml flask.
(16.1 mmol) and 35 ml of DMAc were charged and reacted at 70 ° C. for 4 hours. Unreacted potassium pentenoate and generated potassium bromide in the reaction mixture were removed by water extraction purification to obtain an alkenyl-terminated polymer. The number average molecular weight of the obtained polymer was 11,300 by GPC measurement (mobile phase chloroform, converted to polystyrene), and the molecular weight distribution was 1.12. According to ¹ H-NMR analysis, the number of alkenyl groups per polymer was 1.82.
Was individual.

In a 200 ml pressure-resistant reaction tube, 15 g of the alkenyl-terminated polymer and 1.8 ml of methyldimethoxysilane were added.
(14.5 mmol), 0.26 ml of methyl orthoformate
(2.4 mmol), 10 ^-4 mmol of platinum bis (divinyltetramethyldisiloxane) and 4
The reaction was carried out for a time to obtain a crosslinkable silyl group-containing polymer. The number average molecular weight of the obtained polymer was 11,900 by GPC measurement (mobile phase chloroform, converted to polystyrene), and the molecular weight distribution was 1.12. According to ¹ H-NMR analysis, the number of crosslinkable silyl groups per polymer was 1.4.
There were six. The viscosity was 440 poise.

Comparative Synthesis Example 1 800 g of polyoxypropylene having a number average molecular weight of 8,000 in which an allyl ether group was introduced at 97% of all terminals was placed in a pressure-resistant reaction vessel equipped with a stirrer, and methyldimethoxysilane 19 was added.
g was added. Next, a chloroplatinic acid solution (H ₂ PtCl ₆
8.9 g of 6H ₂ O in isopropyl alcohol 18 m
and 0.34 ml of a solution dissolved in 160 ml of tetrahydrofuran), and reacted at 80 ° C. for 6 hours. Analysis of the amount of residual Si-H groups in the reaction solution by IR revealed that they were almost nonexistent. Also, ¹ H-NM
By R analysis, the number of crosslinkable silyl groups per polymer was about 1.7. The viscosity was 150 poise.

Comparative Synthesis Example 2 In a 200 ml flask, a vinyl polydimethylsiloxane having a molecular weight of 17,200 (DMS-V manufactured by AZMAX)
25: 97 g of unsaturated group equivalent (0.11 eq / kg), 2.3 g (21.4 mmol) of methyldimethoxysilane, and platinum bis (divinyltetramethyldisiloxane) 1
0 ^-3 mmol was added and reacted at 70 ° C for 6 hours. The number average molecular weight of the obtained crosslinkable silyl group-terminated polydimethylsiloxane was 11,900 by GPC measurement (chloroform of mobile phase, converted to polystyrene), and the molecular weight distribution was 2.52. ^{In 1} H-NMR (300 MHz), the peak derived from the unsaturated group disappeared, and the per molecule of the polydimethylsiloxane polymer determined from the intensity ratio of the methyl proton bonded to the silicon atom derived from the polymer main chain and the proton of the methoxysilyl group. The number of crosslinkable silicon groups was 2. The viscosity was 6 poise.

Example 1 100 parts by weight of the crosslinkable silyl group-terminated polymer synthesized in Synthesis Example 1 was combined with 1 part by weight of water and a curing catalyst [U-Nitto Kasei Co., Ltd.
220 (trade name), dibutyltin diacetylacetonate], 3 parts by weight, well mixed, poured into a mold,
A foam was obtained by reducing the pressure. State when a commercially available water-based paint for construction is applied to the obtained foam (paintability)
Table 1 shows the surface state (heat resistance) after curing the foam at 150 ° C. for one day.

Example 2 To 100 parts by weight of the crosslinkable silyl group-terminated polymer synthesized in Synthesis Example 1, 1 part by weight of water and a curing catalyst [U-
220 (trade name), dibutyltin diacetylacetonate], 3 parts by weight and 1 part by weight of chlorofluorocarbon HFC245fa are added and mixed, poured into a mold, and left at room temperature. (Foam). The state (paintability) when a commercially available water-based paint for construction was applied to the obtained foam,
Table 1 shows the surface condition (heat resistance) after curing at 1 ° C. for 1 day.

Example 3 In place of the polymer of Synthesis Example 1 used in Example 1, Synthesis Example 2 was used.
Was used. A foam was obtained in the same manner, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Example 4 In place of the polymer of Synthesis Example 1 used in Example 1, Synthesis Example 3
Was used. A foam was obtained in the same manner, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 1 The polymer of Comparative Synthesis Example 1 was used in place of the polymer of Synthesis Example 1 used in Example 1. A foam was obtained in the same manner, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 2 The polymer of Comparative Synthesis Example 2 was used in place of the polymer of Synthesis Example 1 used in Example 1. A foam was obtained in the same manner, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

[0084]

[Table 1]

As is evident from the results shown in Table 1, the foams of Examples 1 to 4 were excellent in both coatability and heat resistance. On the other hand, Comparative Example 1 had good coatability, but poor heat resistance. Comparative Example 2 had poor coatability but good heat resistance.

[0086]

The present invention comprises a foamable resin composition containing the following two components: (A) a vinyl polymer having at least one crosslinkable silyl group, and (B) a foaming agent. Foamed and cured is excellent in weatherability, heat resistance, paintability, adhesiveness and the like.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuo Shimizu 1-2-80 Yoshida-cho, Hyogo-ku, Kobe City, Hyogo Prefecture Kanebuchi Chemical Industry Co., Ltd. Functional Materials RD Center Kobe Research Laboratory (72) Inventor Kenichi Kitano Hyogo Prefecture 1-280 Yoshida-cho, Hyogo-ku, Kobe-shi Kaneka Chemical Industry Co., Ltd. Functional Materials RD Center Kobe Research Laboratory (72) Inventor Yoshiki Nakagawa 1-2-80 Yoshida-cho, Hyogo-ku, Hyogo-ku, Kobe City, Hyogo Pref. Functional Materials RD Center in Kobe Laboratory

Claims (10)

[Claims] 1. The following two components: (A) a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1), and-[Si (R ¹ ) _2-b (Y) ^{_{b O] m -Si (R 2}} ) 3-a (Y) a (1) [ wherein, R ¹ and R ² are the same or different, an alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms An aryl group, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃
Represents a triorganosiloxy group represented by SiO— (wherein, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms).
A plurality of R's 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. When two or more Y are present, they may be the same or different. a represents 0, 1, 2 or 3. b represents 0, 1, or 2. m shows the integer of 0-19.
However, it satisfies that a + mb ≧ 1. A foamable resin composition containing (B) a foaming agent. 2. The foamable resin composition according to claim 1, wherein the molecular weight distribution of the vinyl polymer (A) is less than 1.8. 3. A method according to claim 1, wherein the vinyl polymer of the component (A) is (meth)
An acrylic polymer according to any one of claims 1 to 2.
Item 10. The foamable resin composition according to item 7. 4. The foamable resin composition according to claim 1, wherein the vinyl polymer as the component (A) is an acrylic polymer. 5. The foamable resin composition according to claim 1, wherein the method for producing the vinyl polymer as the component (A) is a living radical polymerization method. 6. The foamable resin composition according to claim 1, wherein the method for producing the vinyl polymer as the component (A) is an atom transfer radical polymerization method. 7. The vinyl polymer as the component (A) has at least one crosslinkable silyl group represented by the general formula (1) at a terminal of a molecular chain. Item 2. The foamable resin composition according to item 1. 8. A vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1) as the component (A), wherein (1) an organic halide or a sulfonyl halide compound is used as an initiator. A step of synthesizing a vinyl polymer having a halogen atom at its terminal by radically polymerizing a vinyl monomer using a transition metal complex as a catalyst,
(2) A vinyl polymer having a terminal alkenyl group is obtained by reacting a vinyl polymer having a terminal with a halogen atom obtained in the above step (1) with an oxyanion having a alkenyl group to replace halogen. A step of synthesizing, and (3) a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) in a terminal alkenyl group of the vinyl polymer having a terminal alkenyl group obtained in the step (2) The foamable resin composition according to any one of claims 1 to 7, which is a polymer obtained by a step of converting the compound into a substituent containing a crosslinkable silyl group by adding a compound represented by the following formula: 9. A vinyl polymer having a crosslinkable silyl group represented by the general formula (1) of the component (A) is obtained by the following steps: (1) polymerizing a vinyl monomer by a living radical polymerization method. A step of synthesizing a vinyl polymer, and (2) having an alkenyl group at a terminal by reacting the vinyl polymer obtained in the step (1) with a compound having at least two alkenyl groups having low polymerizability. (3) a step of synthesizing a vinyl polymer, and (3) a crosslinking property represented by the general formula (1) to a terminal alkenyl group of the vinyl polymer having a terminal alkenyl group obtained in the step (2). The polymer according to any one of claims 1 to 7, which is a polymer obtained by a step of adding a hydrosilane compound having a silyl group to convert the compound into a substituent having a crosslinkable silyl group. RESIN composition. 10. A foam obtained by foaming and curing the foamable resin composition according to claim 1.