JP2006274084A - Resin composition for gasket molded in situ and the gasket - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellently curable composition for a gasket molded in situ which gives the gasket molded in situ having excellent heat resistance, weatherability, oil resistance (especially brake fluid resistance, coolant resistance) and permanent compression set, and also to provide a gasket molded in situ using the composition. <P>SOLUTION: The composition comprises following components (A) and (B) as essential ingredients. Its cured product has excellent brake fluid resistance or coolant resistance and has mass and volume change rate of at most 50%, measured before and after immersion following the immersion test JIS K 6258 to non-mineral based brake fluid for automobiles specified by JIS K 2233 or the immersion test JIS K 6258 to antifreeze specified by JIS K 2234. The component (A) is a vinyl polymer having at least 2 groups expressed by formula (1), -OC(O)C(R<SP>a</SP>)=CH<SB>2</SB>(R<SP>a</SP>is a hydrogen atom or a 1-20C organic group), in a molecule and at least one of the above groups at a terminal of a molecule. The component (B) is an initiator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a composition for an in-situ molded gasket and an in-situ molded gasket manufactured using the composition. More specifically, the present invention relates to an in-situ molded gasket composition containing a vinyl polymer having a (meth) acryloyl group at a molecular end as an essential component, and an in-situ molded gasket manufactured using the composition.

Acrylic rubber is used as a functional part, a safety part, etc. around the engine of a car because of its heat resistance and oil resistance, and a gasket is one of the large product forms.
However, gaskets can be obtained by kneading fillers, vulcanizing agents, and other compounding agents in unvulcanized rubber, and then vulcanizing and molding. In the case of acrylic rubber, it adheres to the roll during kneading, There are problems with poor curability, such as sometimes difficult to smooth, poor workability such as non-fluidity during molding, slow vulcanization speed, or long post-curing. There are also problems such as the reliability of the seal and the necessity of precision machining of the flange surface.

Although the thing which improved workability and sclerosis | hardenability is also reported (patent document 1), the photocuring in which quick hardening is possible is possible and productivity cannot be improved.
In addition, silicone materials and urethane (meth) acrylate resin as the main component are used as gasket materials. When silicone materials are used, recent high performance coolant and brake fluid are used. In some cases, the resistance to coolant and the brake fluid resistance are not sufficient, for example, the damage is large and the rubber hardness is greatly reduced after immersion. Furthermore, some rubber compositions in which liquid polybutadiene is blended with a tetrafluoroethylene-propylene copolymer exhibit excellent coolant resistance, but an adhesive is required for joining with a member. (Patent Document 2) and the like so far, the sealant alone cannot completely solve the coolant resistance and brake fluid resistance.

On the other hand, when a resin mainly composed of urethane (meth) acrylate resin is used, some of them have excellent oil resistance (Patent Document 3), but have an ether bond or an ester bond in the main chain. There is a problem.
The present inventors have so far reported a polymer having a main chain as an acrylic polymer obtained by living radical polymerization and having a (meth) acryloyl group at its terminal (Patent Documents 4 and 5). The compression set, which is a necessary physical property, is not described.
JP 2000-154370 A JP 2002-249631 A JP-A 64-112 JP 2000-72816 A JP 2000-95826 A

The present invention can provide an in-situ molded gasket excellent in heat resistance, weather resistance, oil resistance, compression set, and the like, and a composition for a curable in-situ molded gasket excellent in curability, and the composition. It is an object of the present invention to provide an in-situ molded gasket manufactured using the same.

The present inventors contain a vinyl polymer having a (meth) acryloyl group and an initiator, and the cured product has a mass and volume change ratio before and after being immersed in the immersion test of JIS K 6258. The present inventors have found that the above problems can be solved by a composition of 50% or less, and have reached the present invention.

That is, this invention relates to the composition for on-site molded gaskets which consists of the following structures, and the on-site molded gasket manufactured using this composition.
(1)
The following (A) component, (B) component is contained as an essential component, and the cured product has a mass before and after being immersed in a JIS K 6258 immersion test for a non-mineral brake fluid for automobiles specified in JIS K 2233 An on-site molded gasket composition having excellent brake fluid resistance, characterized in that the volume change rate is 50% or less.
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl polymer having two or more groups represented by the formula (1) and having one or more groups represented by the general formula (1) at the molecular end thereof,
(B) Initiator.
(2)
In the immersion test of JIS K 6258 with respect to the antifreeze liquid defined in JIS K 2234, the mass and volume change rate before and after immersion are 50, which contains the component (A) and the component (B) as essential components. % Composition for on-site molded gaskets having excellent coolant resistance.
(3)
(A) The composition for on-site molded gaskets in any one of (1)-(2) whose vinyl-type monomer which comprises the principal chain of a component is a (meth) acrylic-type monomer.
(4)
(A) The composition for on-site molded gaskets in any one of (1)-(3) whose vinyl-type monomer which comprises the principal chain of a component is an acrylate-type monomer.
(5)
(A) The vinyl monomer constituting the main chain of the component contains at least two selected from butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate, according to any one of (1) to (4). In-situ molded gasket composition.

(6)
(A) The composition for on-site molded gaskets in any one of (1)-(5) whose ^Ra in General formula (1) is a hydrogen atom or a C1-C20 hydrocarbon group.
(7)
(A) The composition for on-site molded gaskets according to (6), wherein R ^a in the general formula (1) of the component is a hydrogen atom or a methyl group.
(8)
The composition for on-site molded gaskets according to any one of (1) to (7), which is used for sealing a site requiring oil resistance.
(9)
The composition for on-site molded gaskets according to any one of (1) to (8), which is used for sealing a site requiring heat resistance.
(10)
The composition for in-situ molded gaskets according to any one of (1) and (3) to (9), which is used around a brake of an automobile.

(11)
The on-site molded gasket composition according to any one of (2) to (9), which is used for sealing around a radiator of a liquid-cooled internal combustion engine.
(12)
The component (A) is
To the vinyl polymer having a halogen group at the end,
General formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The composition for on-site molded gaskets in any one of (1)-(11) manufactured by making the compound shown by react.
(13)
A vinyl polymer having a halogen group at the end is represented by the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to the ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
(12) The composition for in-situ molded gaskets which has group shown by.
(14)
The component (A) is
To the vinyl polymer having a hydroxyl group at the end,
General formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The composition for on-site molded gaskets in any one of (1)-(11) manufactured by making the compound shown by react.
(15)
The component (A) is
(1) A diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at a terminal,
(2) Residual isocyanate group and general formula (5):
HO-R'- OC (O) C (R ^a ) = CH ₂ (5)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The composition for on-site molded gaskets in any one of (1)-(11) manufactured by making it react with the compound shown by these.

(16)
The composition for on-site molded gaskets according to any one of (1) to (15), wherein the main chain of the component (A) is produced by living radical polymerization of a vinyl monomer.
(17)
The composition for in-situ molded gasket according to (16), wherein the living radical polymerization is atom transfer radical polymerization.
(18)
The composition for in-situ molded gasket according to (17), wherein the transition metal complex which is a catalyst for atom transfer radical polymerization is selected from a complex of copper, nickel, ruthenium or iron.
(19)
The composition for in-situ molded gasket according to (18), wherein the transition metal complex is a copper complex.
(20)
The composition for on-site molded gaskets according to any one of (1) to (15), wherein the main chain of the component (A) is produced by polymerization of a vinyl monomer using a chain transfer agent.

(21)
The composition for in-situ molded gaskets according to any one of (1) to (20), wherein the number average molecular weight of the component (A) is 3000 or more.
(22)
The vinyl polymer as the component (A) is any one of (1) to (21), wherein the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is less than 1.8. For on-site molded gaskets.
(23)
The composition for on-site molded gasket according to any one of (1) to (22), wherein the component (B) is a radical initiator.
(24)
The on-site molded gasket composition according to any one of (1) to (22), wherein the component (B) is an anionic initiator.
(25)
The composition for in-situ molded gasket according to any one of (1) to (22), wherein the component (B) is a redox initiator.

(26)
The composition for in-situ molded gaskets according to any one of (1) to (25), which contains a monomer and / or an oligomer having a radical polymerizable group.
(27)
The composition for in-situ molded gaskets according to any one of (1) to (26), which contains a monomer and / or an oligomer having an anionically polymerizable group.
(28)
The composition for on-site molded gaskets according to any one of (26) to (27), which contains a monomer and / or an oligomer having a (meth) acryloyl group.
(29)
The composition for in-situ molded gasket according to (28), further comprising a monomer and / or an oligomer having a (meth) acryloyl group and a number average molecular weight of 5000 or less.
(30)
An on-site molded gasket comprising the composition for a curable on-site molded gasket according to any one of (1) to (29).
(31)
An in-situ molded gasket obtained by subjecting the composition for a curable in-situ molded gasket according to any one of (1) to (29) to at least one of radical polymerization, anionic polymerization, and oxidation-reduction polymerization.

The composition for in-situ molded gasket of the present invention will be described below.
The composition for in-situ molded gasket of the present invention,
The following (A) component, (B) component is contained as an essential component, and the cured product has a mass before and after being immersed in a JIS K 6258 immersion test for non-mineral brake fluid for automobiles specified in JIS K 2233 In-situ molded gasket composition having excellent brake fluid resistance, characterized by having a volume change rate of 50% or less;
The following (A) component and (B) component are contained as essential components, and in the immersion test of JIS K 6258 with respect to the antifreeze liquid specified in JIS K 2234, the cured product has a mass and volume change rate of 50 before and after immersion. %, It is a composition for in-situ molded gaskets having excellent coolant resistance.
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl polymer having two or more groups represented by the formula (1) and having one or more groups represented by the general formula (1) at the molecular end thereof,
(B) Initiator.

<< (A) component >>
The component (A) is represented by the general formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Is a vinyl polymer having 2 or more groups per molecule, and having 1 or more groups represented by the general formula (1) at the molecular terminals.

The number of groups ((meth) acryloyl group) represented by the general formula (1) in the component (A) is 2 or more per molecule, and 1 or more at the molecular end. Two per molecule are preferred.
Since the side reaction may actually occur when the component (A) is produced, the average number of the (meth) acryloyl group in the produced vinyl polymer mixture is less than 2. May be. In the present invention, when the average value of the number of (meth) acryloyl groups in the actually produced vinyl polymer mixture is 1.1 or more, this mixture is referred to as component (A). That is, the component (A) includes a mixture of vinyl polymers containing a vinyl polymer having two or more (meth) acryloyl groups per molecule and one or more at the molecular end.
From the viewpoint of crosslinking, the average value of the number of the (meth) acryloyl group is preferably 1.5 or more per molecule.
Furthermore, one or more of the (meth) acryloyl group is present at the molecular end, but the position of the other (meth) acryloyl group is not particularly limited. From the viewpoint that the distance between cross-linking points can be increased, a form close to the other molecular end is preferable, and a form close to the other molecular end is particularly preferable.

R ^a in the (meth) acryloyl group represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include 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, a nitrile group, and the like. And the like.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.
Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.
Preferred examples of R ^a include, for example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), —C ₆ H ₅ , — CH ₂ OH, —CN and the like can be mentioned, and preferably —H, —CH ₃ .

(A) There is no limitation in particular as a vinyl-type monomer which comprises the principal chain of a component, A various thing can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2- Perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid diper Fluoromethylmethyl, (meth) acrylic acid 2-perf (Meth) such as fluoromethyl-2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Acrylic monomers; aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and their salts; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; vinyl Silicon-containing vinyl monomers such as trimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; Maleimide monomers such as reimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile Amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene, isoprene, etc. And conjugated dienes such as vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or in combination.

Of these, aromatic vinyl monomers and (meth) acrylic monomers are preferred from the viewpoint of physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, and more preferred are butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. Furthermore, from the viewpoint of oil resistance and the like, it is particularly preferable that the vinyl monomer constituting the main chain includes at least two selected from butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate.

In the present invention, these preferable monomers may be copolymerized with the other monomers, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40% or more. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

The molecular weight distribution of component (A) [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC)] is not particularly limited, but is preferably less than 1.8. More preferably, it is 1.7 or less, more preferably 1.6 or less, particularly preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less.
In the GPC measurement in the present invention, usually, chloroform or tetrahydrofuran is used as a mobile phase, a polystyrene gel column is used, and the molecular weight value is obtained in terms of polystyrene.

The lower limit of the number average molecular weight of the component (A) is preferably 500, more preferably 3000, and the upper limit is preferably 100,000, more preferably 40000. If the molecular weight is less than 500, the original characteristics of the vinyl polymer tend to be hardly expressed, and if it exceeds 100,000, handling tends to be difficult.

<Production method of component (A)>
(A) There is no limitation in particular about the manufacturing method of a component.
The vinyl polymer is generally produced by anionic polymerization or radical polymerization, but radical polymerization is preferred because of the versatility of the monomer or ease of control. Among radical polymerizations, it is preferably produced by living radical polymerization or radical polymerization using a chain transfer agent, and the former is particularly preferable.

The radical polymerization method used for the production of the component (A) is a method in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound, a peroxide or the like as a polymerization initiator. Can be classified into “radical polymerization method” and “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position such as a terminal.

The “general radical polymerization method” is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use this monomer in a considerably large amount. On the contrary, if the monomer is used in a small amount, there is a problem that the proportion of the polymer in which this specific functional group is not introduced increases. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

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

In the “chain transfer agent method”, a polymer having a high functionalization rate can be obtained, but a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is required. There is an economic problem. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and high viscosity can be obtained because of free radical polymerization.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.
Therefore, in the “living radical polymerization method”, a polymer having a narrow molecular weight distribution and a low viscosity can be obtained, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing the vinyl polymer having the specific functional group is more preferable.

Living polymerisation means, in a narrow sense, polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. Pseudo-living polymerization in which is grown while in equilibrium. The definition in the present invention is also the latter.

The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown in Journal of the American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules, 1994, Vol. 27, page 7228, using radical scavengers such as nitroxide compounds, organic halides and the like as initiators and transition metal complexes as catalysts. Atom transfer radical polymerization (ATRP) etc. are mentioned.

Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned “living radical polymerization method”. In addition to the characteristics of "", it has a halogen which is relatively advantageous for functional group conversion reaction at the end, and has a great degree of freedom in designing initiators and catalysts. Therefore, production of vinyl polymers having specific functional groups The method is more preferable.

Examples of the atom transfer radical polymerization method include, for example, Matyjazewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules. 1995, 28, 7901, Science 1996, 272, 866, WO 96/30421 pamphlet, WO 97/18247 pamphlet or Sawamoto et al., Macromolecules 1995, 28, The method described in page 1721 etc. is mentioned.

In the present invention, there is no particular restriction as to which of these methods is used, but basically, a controlled radical polymerization method is used, and a living radical polymerization method is preferred from the viewpoint of ease of control, and particularly an atom transfer radical. A polymerization method is preferred.

First, one of the controlled radical polymerization methods, a polymerization method using a chain transfer agent will be described.
The radical polymerization using a chain transfer agent (telomer) is not particularly limited, but the following two methods are exemplified as a method for obtaining a vinyl polymer having a terminal structure suitable for the present invention.
JP-A-4-132706 discloses a method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent, JP-A-61-271306, JP-A-2594402, This is a method for obtaining a hydroxyl-terminated polymer by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent as disclosed in JP-A-54-47782.

Next, the living radical polymerization method will be described.
First, a method using a radical scavenger (capping agent) such as a nitroxide compound will be described.
In this polymerization method, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Such compounds are not particularly limited, but are cyclic such as 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical. Nitroxy free radicals from hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable.

Specific examples of the nitroxy free radical compound include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl- 1-piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, Examples include 1,1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like.
Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

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

As the radical generator, various compounds can be used, but a peroxide capable of generating a radical under polymerization temperature conditions is preferable.
The peroxide is not particularly limited, but diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, bis Examples include peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctoate, and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable.
Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.

As reported in Macromolecules 1995, 28, 2993, instead of using a radical capping agent and a radical generator together, the following alkoxyamine compound may be used as an initiator. I do not care.

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

There are no particular limitations on the polymerization conditions such as the monomer, solvent, and polymerization temperature used in the polymerization using a radical scavenger such as the nitroxide compound, but it may be the same as that used for the atom transfer radical polymerization described below.

Next, an atom transfer radical polymerization method that is more preferable as the living radical polymerization method used in the present invention will be described.
In this atom transfer radical polymerization method, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having halogen at the α-position or a compound having halogen at the benzyl-position), or halogen A sulfonyl chloride compound or the like is used as an initiator.

For example,
_{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2
(Wherein C ₆ H ₅ is a phenyl group, X is a chlorine atom, a bromine atom or an iodine atom),
^{_{R 3 -C (H) (X}} ) -CO 2 R 4, R 3 -C (CH 3) (X) -CO 2 R 4, R 3 -C (H) (X) -C (O) R 4 _{^{, R 3 -C (CH 3)}} (X) -C (O) R 4
(Wherein R ³ and R ⁴ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X is a chlorine atom, bromine atom or iodine atom) ),
R ³ —C ₆ H ₄ —SO ₂ X
(Wherein R ³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X is a chlorine atom, bromine atom or iodine atom)
Etc.

As an initiator of the atom transfer radical polymerization method, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a structure represented by the general formula (1) at the end of one main chain and the functional group at the other main chain end is produced.
Examples of the functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, and an amide group.

The organic halide having the alkenyl group is not particularly limited. For example, the general formula (6):
^{R 6 R 7 C (X)} -R 8 -R 9 -C (R 5) = CH 2 (6)
(In the formula, R ⁵ is a hydrogen atom or a methyl group, R ⁶ and R ⁷ are a hydrogen atom, 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 others. R ⁸ is —C (O) O— (ester group), —C (O) — (keto group) or o-, m-, p-phenylene group, R ⁹ is a direct bond Or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds, X is a chlorine atom, a bromine atom or an iodine atom)
What is shown by this is illustrated.

Specific examples of the substituents R ⁶ and R ⁷ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.
Examples of the divalent organic group having 1 to 20 carbon atoms that may contain one or more ether bonds of R ⁹ include, for example, 1 to 20 carbon atoms that may contain one or more ether bonds. An alkylene group etc. are mentioned.

Specific examples of the organic halide having an alkenyl group represented by the general formula (6) include
_{XCH 2 C (O) O (} CH 2) n CH = CH 2,
H ₃ CC (H) (X) C (O) O (CH ₂ ) _n CH═CH ₂ ,
(H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n CH═CH ₂ ,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n CH = CH 2,

(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20),
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m CH = CH 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,

(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m CH = CH 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2
(In the above formulas, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1-20, m is an integer of 0-20)
Etc.

The organic halide having an alkenyl group is further represented by the general formula (7):
_{^{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (7)
Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ and X are the same as above, R ¹⁰ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group ) Or o-, m-, p-phenylene group)
The compound shown by these is mentioned.

R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), and in the case of a direct bond, a halogen atom is bonded. A vinyl group is bonded to the carbon, and is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group, a phenylene group or the like as R ¹⁰ , and a direct bond may be used. When R ⁹ is not a direct bond, R ¹⁰ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

If the compound represented by the general formula (7) is specifically exemplified,
_{CH 2 = CHCH 2 X, CH} 2 = C (CH 3) CH 2 X,
_{CH 2 = CHC (H) (} X) CH 3, CH 2 = C (CH 3) C (H) (X) CH 3,
_{CH 2 = CHC (X) (} CH 3) 2, CH 2 = CHC (H) (X) C 2 H 5,
_{CH 2 = CHC (H) (} X) CH (CH 3) 2,
_{CH 2 = CHC (H) (} X) C 6 H 5, CH 2 = CHC (H) (X) CH 2 C 6 H 5,
_{CH 2 = CHCH 2 C (H} ) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 3 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 8 C (H) (X) -CO 2 R,
_{CH 2 = CHCH 2 C (H} ) (X) -C 6 H 5,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -C 6 H 5,
_{CH 2 = CH (CH 2)} 3 C (H) (X) -C 6 H 5
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group)
Etc.

Specific examples of the sulfonyl halide compound having the alkenyl group include
_{o-, m-, p-CH 2} = CH- (CH 2) n -C 6 H 4 -SO 2 X,
_{o-, m-, p-CH 2} = CH- (CH 2) n -O-C 6 H 4 -SO 2 X
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
Etc.

The organic halide having a crosslinkable silyl group is not particularly limited. For example, the general formula (8):
^{R 6 R 7 C (X)} -R 8 -R 9 -C (H) (R 5) CH 2 - [Si (R 11) 2-b (Y) b O] m -Si (R 12) 3- _a (Y) _a (8)
(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are the same as described above, and R ¹¹ and R ¹² are all alkyl groups, aryl groups, aralkyl groups having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). An organosiloxy group, when two or more R ¹¹ or R ¹² are present, they may be the same or different; Y represents a hydroxyl group or a hydrolyzable group; and Y is two or more When present, they may be the same or different, a is 0, 1, 2 or 3, b is 0, 1 or 2, m is an integer from 0 to 19, provided that a + mb ≧ 1 Satisfy)
The following are exemplified.

If the compound represented by the general formula (8) is specifically exemplified,
XCH ₂ C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (OCH 3) 3,
(CH ₃ ) ₂ C (X) C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{XCH 2 C (O) O (} CH 2) n Si (CH 3) (OCH 3) 2,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
_{(CH 3) 2 C (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
(In the above formula, X is a chlorine atom, bromine atom, iodine atom, n is an integer of 0-20),
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (CH 3) (OCH 3) 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2
(Wherein X is a chlorine atom, bromine atom, iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3
(In the above formula, X is a chlorine atom, a bromine atom or an iodine atom)
Etc.

The organic halide having a crosslinkable silyl group is further represented by the general formula (9):
_{^{(R 12) 3-a (}} Y) a Si- [OSi (R 11) 2-b (Y) b] m -CH 2 -C (H) (R 5) -R 9 -C (R 6) ( X) -R ¹⁰ -R ⁷ (9)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , a, b, X, Y are the same as above, m is an integer of 0-19)
What is shown by this is illustrated.

If the compound represented by the general formula (9) is specifically exemplified,
_{(CH 3 O) 3 SiCH 2} CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -C 6 H 5,
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group)
Etc.

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said hydroxyl group, The following are illustrated.
_{HO- (CH 2) n -OC (} O) C (H) (R) (X)
(Wherein X is a chlorine atom, bromine atom or iodine atom, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said amino group, The following are illustrated.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(Wherein X is a chlorine atom, bromine atom or iodine atom, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said epoxy group, The following are illustrated.

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

In order to obtain a vinyl polymer having two or more groups represented by the general formula (1) per molecule at the molecular end, an organic halide or sulfonyl halide compound having two or more starting points is used as an initiator. It is preferable to use as. For example,

Etc.
There is no restriction | limiting in particular in the vinyl-type monomer used in this superposition | polymerization, and all already illustrated can be used suitably.

Further, the transition metal complex used as a polymerization catalyst is not particularly limited, but preferably a metal complex having a central metal of Group 7, Group 8, Group 9, Group 11 or Group 11 of the periodic table, for example, copper, It is a metal complex of nickel, ruthenium and iron. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable.

Specific examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. Is mentioned.
When a copper compound is used, 2,2′-bipyridyl, its derivative, 1,10-phenanthroline, its derivative, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as polyamine can be added.

A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst.
When a ruthenium compound is used as a catalyst, aluminum alkoxides can be added as an activator.
Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistributylphosphine complex ( NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

The polymerization can be carried out without solvent or in various solvents.
Solvent types include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate, butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more.
Moreover, superposition | polymerization can be performed in room temperature-200 degreeC, Preferably it is 50-150 degreeC.

<Functional group introduction method>
The method for producing the component (A) is not particularly limited. For example, a vinyl polymer having a reactive functional group is produced by the method described above, and the reactive functional group is changed to a substituent having a (meth) acryloyl group. It can be manufactured by converting.
Below, the method to convert the terminal of the vinyl polymer which has a reactive functional group into group represented by General formula (1) is demonstrated.

The method for introducing the (meth) acryloyl group at the terminal of the vinyl polymer is not particularly limited, and examples thereof include the following methods.
(Introduction method 1) A vinyl polymer having a halogen group (halogen atom) at the terminal, and the general formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The method by reaction with the compound shown by these.
As a vinyl polymer having a halogen group at the terminal, the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to an ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
Those having a terminal group represented by are preferred.

(Introduction method 2) A vinyl polymer having a hydroxyl group at the terminal, and the general formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The method by reaction with the compound shown by these.
(Introduction method 3) A vinyl-based polymer having a hydroxyl group at the terminal is reacted with a diisocyanate compound to form a residual isocyanate group and the general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The method by reaction with the compound shown by these.

Below, each said method is demonstrated in detail.
[Introduction method 1]
The introduction method 1 is a method by a reaction between a vinyl polymer having a halogen group at the terminal and a compound represented by the general formula (2).
The vinyl polymer having a halogen group at the terminal is not particularly limited, but a vinyl polymer having a terminal group represented by the general formula (3) is preferable.
Examples of the group bonded to the ethylenically unsaturated group of the vinyl monomer in R ¹ and R ² in the general formula (3) include a hydrogen atom, a methyl group, a carbonyl group, a carboxylate group, a toluyl group, a fluoro group, and a chloro group. , Trialkoxysilyl group, phenylsulfonic acid group, carboxylic acid imide group, cyano group and the like.
A vinyl polymer having a halogen group at the terminal, particularly a vinyl polymer having a terminal group represented by the general formula (3), is prepared by using the above-mentioned organic halide or halogenated sulfonyl compound as an initiator and catalyzing a transition metal complex. Is produced by a method of polymerizing a vinyl monomer, or a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, but the former is preferred.

There is no limitation in particular in the compound represented by General formula (2).
Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (2) are the same as those described above, and specific examples thereof are the same as those described above.
M ⁺ in the general formula (2) is a counter cation of an oxyanion, and examples of the type include alkali metal ions and quaternary ammonium ions.

Examples of the alkali metal ion include lithium ion, sodium ion, and potassium ion.
Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, dimethylpiperidinium ion, and the like.
Of these, alkali metal ions are preferable, and sodium ions and potassium ions are more preferable.

The usage-amount of the compound shown by General formula (2) becomes like this. Preferably it is 1-5 equivalent with respect to the terminal group shown by General formula (3), More preferably, it is 1.0-1.2 equivalent.
The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric trimethyl. Amides, acetonitrile and the like are preferably used.
Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 2]
The introduction method 2 is a method by a reaction between a vinyl polymer having a hydroxyl group at the terminal and a compound represented by the general formula (4).
There is no limitation in particular in the compound represented by General formula (4).
Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (4) are the same as those described above, and specific examples thereof are the same as those described above.

The vinyl polymer having a hydroxyl group at the terminal is a method of polymerizing a vinyl monomer using the above-mentioned organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a compound having a hydroxyl group as a chain transfer agent. Is produced by a method of polymerizing a vinyl monomer, but the former is preferred.

Although there is no limitation in particular in the method of manufacturing the vinyl polymer which has a hydroxyl group at the terminal, For example, the following method is illustrated.
(A) When synthesizing a vinyl polymer by living radical polymerization, the general formula (10):
_{^{H 2 C = C (R 13}} ) -R 14 -R 15 -OH (10)
(In the formula, R ¹³ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ¹⁴ is —C (O) O— (ester group) or o-, m- or p-phenylene group, and R ¹⁵ is a direct bond. Or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds)
A method of reacting a compound having a polymerizable alkenyl group and a hydroxyl group in one molecule as a second monomer.

R ¹³ is preferably a hydrogen atom or a methyl group. Further, when R ¹⁴ is an ester group, it is a (meth) acrylate compound, and when R ¹⁴ is a phenylene group, it is a styrene compound. A specific example of R ¹⁵ is the same as the specific example of R ⁹ .
There is no limitation on the timing of reacting a compound having a polymerizable alkenyl group and hydroxyl group in one molecule, but the end of the polymerization reaction or the completion of the reaction of a predetermined monomer is particularly desired when rubber-like properties are expected. Later, it is preferable to react as the second monomer.

(B) When synthesizing a vinyl polymer by living radical polymerization, it has a low polymerizable alkenyl group and hydroxyl group in the molecule as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined monomer. A method of reacting a compound.
Although there is no limitation in particular in the said compound, For example, General formula (11):
_{^{H 2 C = C (R 13}} ) -R 16 -OH (11)
(In the formula, R ¹³ is the same as described above, and R ¹⁶ represents a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds.)
And the like.
A specific example of R ¹⁶ is the same as the specific example of R ⁹ .

Although there is no limitation in particular in the compound shown by General formula (11), The alkenyl alcohol like 10-undecenol, 5-hexenol, and allyl alcohol is preferable from the point that acquisition is easy.

(C) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization by a method as disclosed in JP-A-4-132706. A method of introducing a hydroxyl group at a terminal by hydrolysis or reaction with a hydroxyl group-containing compound.

(D) To a vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization, the general formula (12):
^{M + C - (R 17)} (R 18) -R 16 -OH (12)
(In the formula, R ¹⁶ and M ⁺ are the same as described above, and R ¹⁷ and R ¹⁸ are both an electron-withdrawing group for stabilizing carbanion C ⁻ or one is the electron-withdrawing group, the other is a hydrogen atom, and 1 to 10 carbon atoms. Represents an alkyl group or a phenyl group)
A method in which a halogen atom is substituted by reacting a stabilized carbanion having a hydroxyl group represented by formula (1).

Examples of the electron withdrawing group include —CO ₂ R (ester group), —C (O) R (keto group), —CON (R ₂ ) (amide group), —COSR (thioester group), —CN (nitrile group). ), —NO ₂ (nitro group) and the like, —CO ₂ R, —C (O) R, —CN are particularly preferable. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group.

(E) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization is allowed to react with a metal simple substance or an organometallic compound such as zinc to enolate. A method in which an anion is prepared and then an aldehyde or a ketone is reacted.

(F) A vinyl polymer having at least one halogen atom represented by the general formula (3), preferably a halogen atom at the terminal of the polymer, is represented by the general formula (13):
HO-R ^{< 16 >} -O ^- M ^<+> (13)
(Wherein R ¹⁶ and M ⁺ are the same as above)
A hydroxyl group-containing compound represented by the general formula (14):
HO—R ¹⁶ —C (O) O ⁻ M ⁺ (14)
(Wherein R ¹⁶ and M ⁺ are the same as above)
A method in which the halogen atom is substituted with a hydroxyl group-containing substituent by reacting the hydroxyl group-containing compound represented by formula (1).

In the case where a halogen atom is not directly involved in the method of introducing a hydroxyl group as in (a) to (b), the method of (b) is more preferred because control is easier.
In addition, when a hydroxyl group is introduced by converting a halogen atom of a vinyl polymer having at least one carbon-halogen bond such as (c) to (f), control is easier (f). The method is more preferable.

The usage-amount of the compound shown by General formula (4) becomes like this. Preferably it is 1-10 equivalent with respect to the terminal hydroxyl group of a vinyl type polymer, More preferably, it is 1-5 equivalent.
The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric trimethyl. Amides, acetonitrile and the like are preferably used.
Although reaction temperature does not have limitation in particular, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 3]
In the introduction method 3, a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at the terminal, and the residual isocyanate group and the general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ′ represents a divalent organic group having 2 to 20 carbon atoms)
It is the method by reaction with the compound shown by.

Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (5) are the same as those described above, and specific examples thereof are the same as those described above.
Examples of the divalent organic group having 2 to 20 carbon atoms represented by R ′ in the general formula (5) include an alkylene group having 2 to 20 carbon atoms (ethylene group, propylene group, butylene group, etc.), and 6 to 20 carbon atoms. And an arylene group having 7 to 20 carbon atoms.
Although there is no limitation in particular in the compound shown by General formula (5), As a particularly preferable compound, 2-hydroxypropyl methacrylate etc. are mentioned.
The vinyl polymer having a hydroxyl group at the terminal is as described above.

There is no particular limitation on the diisocyanate compound, and any conventionally known one can be used. Specific examples include toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogen. Xylylene diisocyanate, isophorone diisocyanate and the like. These may be used alone or in combination of two or more. Moreover, you may use block isocyanate. From the viewpoint of obtaining better weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

The amount of the diisocyanate compound used is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, relative to the terminal hydroxyl group of the vinyl polymer.
The usage-amount of the compound shown by General formula (5) becomes like this. Preferably it is 1-10 equivalent with respect to a residual isocyanate group, More preferably, it is 1-5 equivalent.
The reaction solvent is not particularly limited, but an aprotic solvent is preferable.
Although there is no limitation in particular in reaction temperature, Preferably it is 0-250 degreeC, More preferably, it is 20-200 degreeC.

<< (B) component >>
(B) Although there is no limitation in particular as an initiator of a component, a radical initiator, an anionic initiator, a redox initiator, etc. are mentioned.
The radical initiator, the anionic initiator, and the redox initiator may be used alone or as a mixture of two or more, but when used as a mixture, various initiators may be used. It is preferable that the usage-amount of exists in each range mentioned later.

For heat curing, a thermal cleavage type radical initiator is used.
As the thermal cleavage type radical initiator, a peroxide-based initiator is preferable.
The peroxide is not particularly limited, but diacyl peroxides such as benzoyl peroxide and lauroyl peroxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diisopropyl peroxydicarbonate, Examples include peroxycarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate; alkyl peresters such as t-butylperoxyoctoate and t-butylperoxybenzoate. In particular, benzoyl peroxide is preferable.
Furthermore, a radical generator such as a radical-generating azo compound such as azobisisobutyronitrile may be used in place of the peroxide.

0.001-10 weight part is preferable with respect to 100 weight part of (A) component, and, as for the addition amount of the said thermal polymerization initiator, 0.01-5 weight part is more preferable.
The said initiator may be used independently or may use 2 or more types together.

When curing with active energy rays, it is preferable to contain a photopolymerization initiator.
Examples of the photo radical initiator include acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2, 2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoyl, benzoin Ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl -Ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like.

These initiators may be used alone or in combination with other compounds. Specifically, combinations with amines such as diethanolmethylamine, dimethylethanolamine and triethanolamine, further combinations with iodonium salts such as diphenyliodonium chloride, and combinations with pigments and amines such as methylene blue, etc. Can be mentioned.

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

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

The anionic initiator is not particularly limited, and examples thereof include a photoanionic initiator.
Specific examples of the photoanion initiator include 1,10-diaminodecane, 4,4′-trimethylenedipiperazine, carbamates and derivatives thereof, cobalt-amine complexes, aminooxyiminos, ammonium borates and the like. It is done.

The addition amount of the photopolymerization initiator is not particularly limited since it only needs to slightly functionalize the system, but is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of component (A). 0.01 to 5 parts by weight is more preferable.
The said initiator may be used independently or may use 2 or more types together.

The active energy ray source is not particularly limited, but depending on the nature of the photopolymerization initiator, for example, high-pressure mercury lamp, low-pressure mercury lamp, electron beam irradiation device, halogen lamp, light-emitting diode, semiconductor laser, etc. Irradiation etc. are mentioned.

For use at room temperature curing, a redox initiator is used.
Suitable redox initiators include, but are not limited to, persulfate initiators (potassium persulfate, sodium persulfate, ammonium persulfate, etc.) and reducing agents (sodium metabisulfite, bisulfite) Combination of organic peroxide and tertiary amine, such as benzoyl peroxide and dimethylaniline; Combination of organic hydroperoxide and transition metal, such as cumene hydroperoxide and cobalt naphthate Is mentioned.
Other initiators include, but are not limited to, pinacol such as tetraphenyl 1,1,2,2-ethanediol.

As addition amount of a redox-type initiator, 0.001-10 weight part is preferable with respect to 100 weight part of (A) component, and 0.01-5 weight part is more preferable.
The said initiator may be used independently or may use 2 or more types together.

<< Composition for on-site molded gasket >>
The composition for in-situ molded gaskets of the present invention is a composition containing the above component (A) and component (B) as essential components.
The composition for on-site molded gasket of the present invention may be used in combination with a polymerizable monomer and / or oligomer for the purpose of improving surface curability, imparting toughness, and improving workability by reducing viscosity. it can.
Furthermore, you may mix | blend various additives etc. in order to adjust a physical property with the composition for on-site molded gaskets of this invention as needed.

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

Examples of the radical polymerizable group include (meth) acryloyl group such as (meth) acryl group, styrene group, acrylonitrile group, vinyl ester group, N-vinylpyrrolidone group, acrylamide group, conjugated diene group, vinyl ketone group, and chloride. A vinyl group etc. are mentioned. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.

Examples of the anionic polymerizable group include a (meth) acryloyl group such as a (meth) acryl group, a styrene group, an acrylonitrile group, an N-vinylpyrrolidone group, an acrylamide group, a conjugated diene group, and a vinyl ketone group. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.

Specific examples of the monomer include (meth) acrylate monomers, cyclic acrylates, styrene monomers, acrylonitrile, vinyl ester monomers, N-vinyl pyrrolidone, acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, vinyl halides. -A vinylidene halide monomer, a polyfunctional monomer, etc. are mentioned.

(Meth) acrylate monomers include 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, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate , Phenyl (meth) acrylate, toluyl (meth) acrylate, (meth) acrylic Benzyl, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, ( (Meth) acrylic acid glycidyl, (meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethylmethyl, (meta ) 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate , Perfluoromethyl (meth) acrylate, (meth) Diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, Examples include (meth) acrylic acid 2-perfluorohexadecylethyl. Moreover, the compound etc. which are shown by the following Formula can also be mention | raise | lifted. In the following formula, n represents an integer of 0-20.

Examples of the styrenic monomer include styrene and α-methylstyrene.
Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl butyrate and the like.
Examples of acrylamide monomers include acrylamide and N, N-dimethylacrylamide.
Examples of the conjugated diene monomer include butadiene and isoprene.
Examples of the vinyl ketone monomer include methyl vinyl ketone.
Examples of the vinyl halide / vinylidene halide monomer include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide.

Multifunctional monomers include trimethylolpropane triacrylate, neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, dipentaerythritol polyhexanolide hexa Chlorate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1 , 3-dioxane, tetrabromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetra Chi glycol diacrylate, 1,9-nonanediol diacrylate, and ditrimethylolpropane tetraacrylate.

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

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

The amount of the polymerizable monomer and / or oligomer used is from 100 parts by weight of the component (A) (hereinafter also simply referred to as “parts”) from the viewpoint of improving surface curability, imparting toughness, and workability by reducing viscosity. 1 to 200 parts is preferable, and 5 to 100 parts is more preferable.

<Reinforcing silica>
Reinforcing silica may be added to the in-situ molded gasket composition of the present invention from the viewpoint of improving the strength of the cured product.
Examples of the reinforcing silica include fumed silica and precipitated silica. Among these, those having a particle diameter of 50 μm or less and a specific surface area of 80 m ² / g or more are preferable from the viewpoint of reinforcing effect. In addition, the measuring method of a specific surface area is as the below-mentioned.

Further, surface-treated silica such as organosilane, organosilazane, diorganocyclopolysiloxane and the like is more preferable because it easily exhibits fluidity suitable for molding.
As a more specific example of the reinforcing silica, there is no particular limitation. However, Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Silica Industry Co., Ltd., which is one of precipitated silicas. Nipsil and the like.

The reinforcing silica may be used alone or in combination of two or more.
Although there is no restriction | limiting in particular in the addition amount of reinforcing silica, Preferably it is 0.1-100 parts with respect to 100 parts of (A) component, More preferably, it is 0.5-80 parts, More preferably, it is 1-50 parts. It is. When the amount is less than 0.1 part, the effect of improving the reinforcing property may not be sufficient, and when it exceeds 100 parts, the workability of the on-site molded gasket composition may be deteriorated.

<Filler>
In addition to the reinforcing silica, various fillers may be used in the on-site molded gasket composition of the present invention as necessary.
The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, dolomite, silicic anhydride, Reinforcing fillers such as hydrous silicic acid and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, bengara, Fillers such as fine aluminum powder, flint powder, zinc oxide, activated zinc white, zinc powder, zinc carbonate and shirasu balloon; fibrous fillers such as asbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber, etc. Is mentioned. Of these fillers, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. In addition, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. may be added. it can.

In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient. The larger the specific surface area value, the greater the effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product. Moreover, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent. When surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved as compared with the case of using non-surface-treated calcium carbonate. It is considered that the effect of improving the sex is further improved.

Examples of the surface treatment agent include organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid. Sodium salts and potassium salts of these fatty acids, and alkyl esters of these fatty acids.
Specific examples of surfactants include sodium anion surfactants such as polyoxyethylene alkyl ether sulfates and long-chain alcohol sulfates, sulfate-type anionic surfactants such as potassium salts, alkylbenzene sulfonic acids, alkylnaphthalene sulfonic acids, paraffins Examples thereof include sulfonic acid type anionic surfactants such as sodium salts and potassium salts such as sulfonic acid, α-olefin sulfonic acid and alkylsulfosuccinic acid.

The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight (hereinafter referred to as “%”) with respect to calcium carbonate, and more preferably in the range of 1 to 5%. If the treatment amount is less than 0.1%, the workability, adhesiveness and weatherability may not be sufficiently improved. If the treatment amount exceeds 20%, the storage stability of the in-situ molded gasket composition may be insufficient. May decrease.

Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is used when particularly improving effects such as thixotropy of the compound, breaking strength of the cured product, elongation at break, adhesion and weather resistance adhesion are expected. Is preferred.
On the other hand, heavy calcium carbonate may be added for the purpose of lowering the viscosity of the compound, increasing the amount, reducing costs, etc. When using this heavy calcium carbonate, the following may be added as necessary. Can be used.

Heavy calcium carbonate is obtained by mechanically pulverizing and processing natural chalk (chalk), marble, limestone, and the like. There are dry and wet methods for pulverization methods, but wet pulverized products are often not preferred because they often deteriorate the storage stability of the in-situ molded gasket composition of the present invention. Heavy calcium carbonate becomes a product having various average particle diameters by classification. There is no particular limitation, but when the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product is expected, the specific surface area value is 1.5 m ² / g or more and 50 m ² / g or less. , more preferably from ^2m 2 / g or more ^{50 m} 2 / g or less, more preferably 2.4 m ² / g or more ^{50m 2 / g, 3m 2 /} g or more ^{50 m} 2 / g or less is particularly preferred. When the specific surface area is less than 1.5 m ² / g, the improvement effect may not be sufficient. Of course, this is not the case when the viscosity is simply lowered or only for the purpose of increasing the viscosity.

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

These fillers may be used alone or in combination of two or more according to the purpose and necessity. Although not particularly limited, for example, when heavy calcium carbonate with a specific surface area value of 1.5 m ² / g or more and colloidal calcium carbonate are combined, the increase in the viscosity of the compound is moderately suppressed. The effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product can be greatly expected.

When the filler is used, the addition amount is preferably 5 to 1000 parts, more preferably 20 to 500 parts, with respect to 100 parts of component (A), It is particularly preferable to use in the range of 40 to 300 parts. When the blending amount is less than 5 parts, the effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product may not be sufficient. Workability may be reduced. A filler may be used independently and may be used together 2 or more types.

<Adhesive resin>
The composition for in-situ molded gaskets of the present invention is preferably composed mainly of a (meth) acrylic polymer, so that it is not always necessary to add an adhesion-imparting resin. Things can be used. Specific examples include phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin, coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin and the like.
The amount of the adhesion-imparting resin used is preferably 0.1 to 100 parts with respect to 100 parts of the component (A) from the viewpoint of the balance between mechanical properties, heat resistance, oil resistance and adhesiveness of the cured product.

<Anti-aging agent>
An anti-aging agent may be blended with the composition for in-situ molded gasket of the present invention in order to adjust physical properties.
An acrylic polymer is originally a polymer excellent in heat resistance, weather resistance, and durability, and therefore, an anti-aging agent is not necessarily required, but a conventionally known antioxidant and light stabilizer may be appropriately used. it can. In addition, the anti-aging agent can be used for polymerization control during polymerization, and physical properties can be controlled.

Various types of antioxidants are known, and are described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242), issued by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.
Examples of the antioxidant include thioethers such as MARK PEP-36 and MARK AO-23 (all are manufactured by Asahi Denka Co., Ltd.); Irgafos 38, Irgafos 168, Irgafos P-EPQ (all are Ciba Specialty And phosphorous antioxidants such as Chemicals Co., Ltd .; hindered phenolic compounds, and the like. Of these, hindered phenol compounds as shown below are preferred.

Specific examples of the hindered phenol compound include the following. 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α methylbenzyl) phenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4, 4′-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol-bis- [3- (3- t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1 , 3,5-triazine, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-) t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-to Limethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl) calcium, tris -(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N'-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-tert-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2 -[2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyl Enyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5 -Chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3 5-Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6- Ntamechiru 4-piperidyl), 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate, and the like.

In terms of trade names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above Also manufactured by Ouchi Shinsei Chemical Co., Ltd.), MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO- 80, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all manufactured by Asahi Denka Co., Ltd.), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024 , IRG NOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all are manufactured by Ciba Specialty Chemicals Co., Ltd.), Sumitizer GA-80 (and above, any Can also be exemplified by, but not limited to, Sumitomo Chemical Co., Ltd.).

Furthermore, a monoacrylate phenolic antioxidant having both an acrylate group and a phenol group, a nitroxide compound, and the like can be given.
Examples of the monoacrylate phenol-based antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name Sumilyzer GM), 2 , 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (trade name Sumitizer GS) and the like.

Nitroxide compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radicals and 2,2,5,5-substituted-1-pyrrolidinyloxy radicals, cyclic hydroxyamines, etc. The nitroxy free radicals from are illustrated. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable.
Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like.
Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

Antioxidants may be used in combination with light stabilizers, and when used together, the effects are further exerted, and the heat resistance may be particularly improved. Tinuvin C353, Tinuvin B75 (all of which are manufactured by Nippon Ciba Geigy Co., Ltd.) and the like in which an antioxidant and a light stabilizer are mixed in advance may be used.

When using a vinyl polymer having a (meth) acryloyl group in the molecule to produce a cured product by photo radical curing, the polymerization proceeds quickly, so that it is difficult to control and the polymerization is excessive. There are many cases where the mechanical strength is insufficient, such as being in an overcrosslinked state and the obtained cured product does not exhibit sufficient elongation. As a method for controlling the polymerization, by making the functional group involved in the polymerization a methacryloyl group, the polymerizability can be lowered as compared with the case of the acryloyl group, but in this case, the polymerizability may be extremely lowered. Many are not practical. In general, a polymerization inhibitor may be used, but this is for the purpose of suppressing the polymerization itself and is not suitable for controlling the polymerization. On the other hand, an anti-aging agent may be added to improve the heat resistance and weather resistance of the obtained cured product, but this is not used for the purpose of improving the initial physical properties of the cured product.
The monoacrylate phenol-based antioxidant can not only be used as an antioxidant but also can control polymerization and can improve the elongation of a cured product. Since the physical properties of the cured product can be easily controlled, the same examples as described above are exemplified. The said monoacrylate phenolic antioxidant may be used independently and may be used in combination of 2 or more type.

Although the usage-amount of said various antioxidants including a monoacrylate phenolic antioxidant is not specifically limited, For the purpose of giving a good effect on the mechanical property of the hardened | cured material obtained, it adds to 100 parts of (A) component. On the other hand, 0.01 part or more is preferable and 0.05 part or more is more preferable. Moreover, 5.0 parts or less are preferable, 3.0 parts or less are more preferable, and 2.0 parts or less are more preferable.

<Plasticizer>
You may mix | blend a plasticizer with the composition for in-situ molded gaskets of this invention.
As a plasticizer, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, etc. Non-aromatic dibasic acid esters; esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphate esters such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; alkyl diphenyl and partial water And hydrocarbon oils such as terphenyl. These can be used alone or in admixture of two or more, but are not necessarily required. In addition, these plasticizers can also be mix | blended at the time of polymer manufacture.
The amount of the plasticizer used is preferably 5 to 800 parts with respect to 100 parts of the component (A) from the viewpoint of imparting elongation, workability, and preventing bleeding from the cured product.

<Solvent>
An organic solvent may be added to the in-situ molded gasket composition of the present invention from the viewpoints of workability during coating, drying before and after curing, and the like.
As the organic solvent, those having a boiling point of 50 to 180 ° C. are usually preferable because of excellent workability during coating and drying before and after curing. Specifically, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol; methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, etc. Ester solvents; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; and cyclic ether solvents such as dioxane. These solvents may be used alone or in combination of two or more.
The amount of the solvent used is preferably 1 to 900 parts with respect to 100 parts of component (A) from the viewpoint of the balance of the finished product, workability, and drying.

<Adhesion improver>
Various adhesion improvers may be added to the on-site molded gasket composition of the present invention in order to improve adhesion to various supports (plastic film or the like).
Examples of adhesion improvers include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropyl methyl diisopropenoxy silane, γ-glycidoxy propyl methyl dimethoxy silane, γ-glycidoxy propyl trimethoxy silane, vinyl trimethoxy silane, vinyl dimethyl methoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-mercaptopro Le trimethoxysilane, .gamma.-mercaptopropyl alkoxysilanes having a functional group such as a methyl dimethoxy silane; silicone varnishes; polysiloxanes and the like.
From the viewpoint of the balance between mechanical properties (elongation and strength) and adhesiveness of the cured product, the amount of the adhesion improver used is preferably 0.1 to 20 parts with respect to 100 parts of component (A).

<Preparation of on-site molded gasket composition>
The in-situ molded gasket composition of the present invention can be prepared as a one-pack type in which all blending components are blended and sealed in advance, and the A liquid from which only the initiator is removed and the initiator as a filler, plasticizer, solvent, etc. It can also be prepared as a two-component type in which the liquid B mixed with is mixed just before molding.

<Curing method>
The composition for in-situ molded gasket of the present invention can be cured at normal temperature or by heating, active energy rays such as UV or electron beam, or active energy such as heat. In order to obtain good curability, brake fluid resistance, and coolant resistance, the active energy ray is particularly preferably cured with an active energy ray such as UV or electron beam.

<< on-site molded gasket >>
The in-situ molded gasket of the present invention is composed of the above-mentioned composition for in-situ molded gasket. Moreover, it is preferable that the in-situ molded gasket of this invention is a thing obtained by performing at least 1 sort (s) of radical polymerization, anion polymerization, and oxidation-reduction polymerization for the said composition for on-site molding gaskets.

(B) When using a photoinitiator as a component, it can be hardened by irradiating light or an electron beam with an active energy ray source.
Although there is no limitation in particular as an active energy ray source, According to the property of the photoinitiator to be used, a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation apparatus, a halogen lamp, a light emitting diode, a semiconductor laser, a metal halide etc. are mentioned, for example.
When a photopolymerization initiator is used as the component (B), the curing temperature is preferably 0 ° C to 150 ° C, more preferably 5 ° C to 120 ° C.
When a thermal polymerization initiator is used as the component (B), the curing temperature varies depending on the type of the thermal polymerization initiator used, the component (A), the other compound added, etc., but usually 50 ° C to 250 ° C. Preferably, 70 ° C to 200 ° C is more preferable.
When a redox initiator is used as the component (B), the curing temperature is preferably −50 ° C. to 250 ° C., more preferably 0 ° C. to 180 ° C.

An in-situ molded gasket obtained by curing the on-site formed gasket composition of the present invention on the spot at room temperature or by heating or active energy sufficiently satisfies the required heat resistance and sealing properties, and is specified in JIS K 2233. In the immersion test of JIS K 6258 for non-mineral brake fluid for use, the mass and volume change rate before and after immersion are 50% or less.
In addition, in order to sufficiently satisfy the required heat resistance and sealing properties, the on-site molded gasket has a mass and volume change rate before and after being immersed in the JIS K 6258 immersion test for antifreeze liquid defined in JIS K 2234. Is 50% or less.

The “non-mineral brake fluid for automobiles defined in JIS K 2233” in the present invention is a medium for obtaining the braking force by transmitting the depression force of the brake pedal to the disc rotor through the brake cylinder. Ingredients are broadly classified into glycol and silicone.
The “antifreeze liquid defined in JIS K 2234” is an antifreeze liquid mainly composed of ethylene glycol used for preventing freezing of the cooling liquid for a liquid-cooled internal combustion engine and preventing corrosion of the cooling mechanism.
Further, “immersion test of JIS K 6258” means that the entire surface of the cured vinyl polymer is immersed in the non-mineral brake fluid or antifreeze for automobiles, and the mass and volume before and after immersion. Etc. are measured.
In the immersion test, the mass change rate before and after immersion is 50% or less, preferably 30% or less, more preferably 20% or less.
The volume change rate before and after immersion is 50% or less, preferably 30% or less, more preferably 20% or less.

<< Usage >>
The composition for on-site formed gasket and the on-site molded gasket of the present invention include a seal for a part that requires oil resistance and heat resistance, specifically, a seal around a brake of an automobile, a seal of an oil pan joint surface of an automobile, a liquid It is suitably used for a seal around a radiator of a cold internal combustion engine.

<Best Mode for Carrying Out the Invention>
The composition for an on-site gasket of the present invention contains the following component (A) and component (B) as essential components, and the cured product is
In the JIS K 6258 immersion test for non-mineral brake fluids for automobiles specified in JIS K 2233, the mass before and after immersion, the volume change rate is 50% or less, or
In the immersion test of JIS K 6258 with respect to the antifreeze liquid defined in JIS K 2234, the mass and volume change rate before and after immersion are 50% or less.
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl polymer having two or more groups represented by the formula (1) and having one or more groups represented by the general formula (1) at the molecular end thereof,
(B) Initiator.
The polymer of component (A) is an acrylate polymer, and the main chain is preferably produced by living radical polymerization, and further by atom transfer radical polymerization. As the component (B), a radical initiator, an anionic initiator, and a redox initiator are preferable. From the viewpoint of improving the strength of the cured product, imparting elongation, improving workability, and the like, it is effective to add an acrylate monomer. In order to obtain good curability, brake fluid resistance, and coolant resistance, the on-site molded gasket composition of the present invention is preferably cured by normal temperature, heating, active energy rays (UV, electron beam, etc.) and the like. .

<Brake fluid>
What is brake fluid?
5-30 base polymer (polyglycol) components of polyoxypropylene glycol, polyoxypropylene triol, poly (oxyethylene oxypropylene) glycol monoalkyl ether, poly (oxyethylene oxypropylene) triol, polyoxyethylene glycol weight%,
Diethylene glycol monomethyl ether (DEGME), triethylene glycol monomethyl ether (TEGME), diethylene glycol monoethyl ether (DEGEE), triethylene glycol monoethyl ether (TEGEE), diethylene glycol monobutyl ether (DEGBE), triethylene glycol monobutyl ether (TEGBE), Polyethylene glycol monoalkyl ether, dipropylene glycol monomethyl ether, polypropylene glycol monoalkyl ether, poly (oxyethylene oxypropylene) glycol monoalkyl ether, boric acid ester of triethylene glycol monoalkyl ether, poly (oxyethylene oxypropylene) Of glycol monoalkyl ether Of c acid ester, a solvent (glycol ether) component 70 to 99 wt%,
2,6-di-t-butyl-p-cresol, 4,4′-butylidenebis (6-t-butyl-m-cresol), pt-butylcresol, β-naphthylamine, tetrakis [methylene (3,5 -Di-t-butyl-4-hydroxyhydrocinnamate)] an antioxidant comprising methane, and a rust inhibitor comprising 2-mercaptobenzothiazole, triethanolamine, n-dibutylamine, dicyclohexylamine, and additives As 0.5-2.0 wt%,
A composition that imparts lubricity to a brake oil.
It is characterized by maintaining viscosity at high temperature, preventing leakage from the seal part, low evaporability, and low viscosity at low temperature.

<Coolant>
The coolant is an additive solution for a radiator, comprising 85% by weight or more of ethylene glycol or propylene glycol; 10% by weight or less of an additive such as an inorganic potassium salt or potassium phosphate; 5% by weight or less of water.
It has an overheat prevention effect, a rust prevention effect, and a bubble suppression effect, and is used in an aqueous solution of 25 to 60% by volume.

The on-site molded gasket composition of the present invention is a normal temperature, heating or active energy curable type, and by using the composition, it has excellent curability, heat resistance, weather resistance, oil resistance, compression set, etc. An excellent on-site gasket can be obtained.

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, the number average molecular weight and the molecular weight distribution (ratio of the weight average molecular weight to the number average molecular weight) were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). A GPC column filled with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.
In the following examples, the average number of terminal (meth) acryloyl groups is the number of (meth) acryloyl groups introduced per molecule of the polymer, and is based on the number average molecular weight determined by ¹ H-NMR analysis and GPC. Calculated.
In the following examples, “part” represents “part by weight”.

Production Example 1 (Synthesis of poly (acryloyl group) -terminated poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate))
Cuprous bromide as catalyst, pentamethyldiethylenetriamine as ligand, diethyl-2,5-dibromoadipate as initiator, n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate in 25 / mole Polymerized at a composition of 46/29, monomer / initiator ratio = 160, and a terminal brominated poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) having a number average molecular weight of 19,800 and a molecular weight distribution of 1.13 )
400 g of this polymer was dissolved in N, N-dimethylacetamide (400 mL), 10.7 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 6 hours under a nitrogen atmosphere. A mixture of butyl / ethyl acrylate / 2-methoxyethyl acrylate) (hereinafter referred to as polymer [1]) was obtained. After N, N-dimethylacetamide in the mixed solution was distilled off under reduced pressure, toluene was added to the residue, and the insoluble matter was removed by filtration. Toluene in the filtrate was distilled off under reduced pressure to purify the polymer [1].
The number average molecular weight of the purified acryloyl group both-end polymer [1] is 20300, the molecular weight distribution is 1.14, and the average terminal acryloyl group number is 1.8 (that is, the introduction rate of acryloyl group at the terminal is 90%). there were.

Production Example 2 (Synthesis of poly (acryloyl group) -terminated poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate))
Cuprous bromide as catalyst, pentamethyldiethylenetriamine as ligand, diethyl-2,5-dibromoadipate as initiator, n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate in 25 / mole Polymerized at a ratio of 46/29, monomer / initiator ratio = 120, a terminal bromine group poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) having a number average molecular weight of 16500 and a molecular weight distribution of 1.13 was obtained. Obtained.
400 g of this polymer was dissolved in N, N-dimethylacetamide (400 mL), 10.7 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 6 hours under a nitrogen atmosphere. A mixture of butyl / ethyl acrylate / 2-methoxyethyl acrylate) (hereinafter referred to as polymer [2]) was obtained. After N, N-dimethylacetamide in the mixed solution was distilled off under reduced pressure, toluene was added to the residue, and the insoluble matter was removed by filtration. The toluene in the filtrate was distilled off under reduced pressure to purify the polymer [2].
The number average molecular weight of the acryloyl group-terminated polymer [2] after purification is 16900, the molecular weight distribution is 1.14, and the average number of terminal acryloyl groups is 1.8 (that is, the introduction rate of acryloyl groups at the terminals is 90%). there were.

Production Example 3 (Synthesis of acryloyl group-terminated poly (n-butyl acrylate))
Polymerization of n-butyl acrylate using cuprous bromide as catalyst, pentamethyldiethylenetriamine as ligand, diethyl-2,5-dibromoadipate as initiator, and terminal bromine having a number average molecular weight of 10800 and a molecular weight distribution of 1.15 The base poly (n-butyl acrylate) was obtained.
300 g of this polymer was dissolved in N, N-dimethylacetamide (300 mL), 8.3 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 3 hours in a nitrogen atmosphere, and acryloyl group-terminated poly (n-butyl acrylate) was added. ) (Hereinafter referred to as polymer [3]). After N, N-dimethylacetamide in the mixed solution was distilled off under reduced pressure, toluene was added to the residue, and the insoluble matter was removed by filtration. The toluene in the filtrate was distilled off under reduced pressure to purify the polymer [3].
The average terminal acryloyl group number of the polymer [3] after purification was 2.0.

Example 1
To 100 parts of the polymer [1] obtained in Production Example 1, 1 part of Irgacure 184 (1-hydroxycyclohexyl-phenyl ketone, manufactured by Ciba Specialty Chemicals), Irgacure 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine) 0.5 parts of oxide, manufactured by Ciba Specialty Chemicals), 1 part of Irganox 1010 (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals) are fully added. To obtain a composition for in-situ molded gasket.
Next, the obtained in-situ molded gasket composition was irradiated with light through a metal halide lamp (80 W / cm, irradiation distance 15 cm, belt speed 1.0 m / min) three times, and cured in a sheet form having a thickness of about 2 mm. I got a thing.
A No. 3 dumbbell of the obtained cured product was produced, and tensile properties were measured using this. Further, the obtained cured product No. 3 dumbbell was immersed in brake fluid Seken BF3 (manufactured by Meiji Sangyo) at room temperature for 3 days, and then the tensile properties were measured.

Example 2
A curable composition and a cured product were produced in the same manner as in Example 1 except that 20 parts of Ebecryl 3708 (epoxy acrylate, manufactured by Daicel UCB) was further added.
In addition to the test and measurement of Example 1, the obtained cured product No. 3 dumbbell was immersed in Toyota genuine LLC as a coolant at 150 ° C. for 3 days, and then the tensile properties were measured.

Example 3
A curable composition and a cured product were obtained in the same manner as in Example 1 except that the polymer [2] was used instead of the polymer [1].
A No. 3 dumbbell of the obtained cured product was produced, and tensile properties were measured using this. In addition, the obtained cured product No. 3 dumbbell was immersed in Toyota genuine LLC / water = 50/50 as a coolant liquid at 125 ° C. for 3 days, and then the tensile properties were measured.

Example 4
A curable composition and a cured product were obtained in the same manner as in Example 1 except that the polymer [3] was used instead of the polymer [1].
A No. 3 dumbbell of the obtained cured product was produced, and tensile properties were measured using this. In addition, the obtained cured product No. 3 dumbbell was immersed in Toyota genuine LLC / water = 50/50 as a coolant liquid at 125 ° C. for 3 days, and then the tensile properties were measured.

Comparative Example 1
100 parts of UA-340P (urethane acrylate, manufactured by Kyoeisha Chemical Co., Ltd.), 0.5 part of 2,2-diethoxyacetophenone, and 1.0 part of Irganox 1010 (manufactured by Ciba Specialty Chemicals) were added to prepare an on-site molded gasket composition.
Using the resulting composition, a cured product was produced in the same manner as in Example 1, and each physical property was measured. Further, in addition to the test of Example 1, the obtained cured product No. 3 dumbbell was immersed in Toyota genuine LLC as a coolant at 150 ° C. for 3 days, and then the tensile properties and the gel fraction were measured.

In the above Examples and Comparative Examples, tests and measurements of each physical property were performed as follows. The results are shown in Table 1.
[Tensile properties]
Using No. 3 dumbbells of cured products obtained in the above Examples and Comparative Examples, Shimadzu Autograph AG-2000A was used, and tensile properties were performed in accordance with JIS K 7113 (measurement conditions: 23 ° C. × 55 % RH, tensile speed 200 mm / min). M30 is 30% modulus (strength at 30% elongation), M50 is 50% modulus, M100 is 100% modulus, TB is strength at break, and EB is elongation at break.

[Gel fraction]
The cured products obtained in the above Examples and Comparative Examples were immersed in toluene at room temperature for 1 day, and the residual weight percentage after drying was measured to determine the gel fraction.

[Volume change rate, mass change rate]
The cured products obtained in the examples and comparative examples were immersed in the brake fluid liquid or the coolant liquid under the above conditions, and then the mass and volume were measured, and the rate of change from the initial value was calculated.

[Compression set]
Using the cured products obtained in the above Examples and Comparative Examples, after compressing 25% for 150 ° C. for 70 hours in accordance with JIS K 6262, the strain (%) was 23 ° C. × 55% R.D. H. Measured under the atmosphere of

From the results shown in Table 1, in the brake fluid resistance test, compared with the urethane acrylate of Comparative Example 1, in Examples 1 and 2, the reduction rate of EB (elongation at break) of the dumbbell before and after the immersion test was small. In the coolant resistance test, the decrease rate of M50 (strength at 50% elongation) before and after the immersion test in Example 2 was small.
From the above, it can be seen that the cured product obtained from the on-site molded gasket composition of the present invention is excellent in brake fluid resistance and coolant resistance.

The on-site molded gasket composition of the present invention is a normal temperature, heating or active energy curable type, and by using the composition, it has excellent curability, heat resistance, weather resistance, oil resistance, compression set, etc. An excellent on-site gasket can be obtained.

Claims (31)

The following (A) component, (B) component is contained as an essential component, and the cured product has a mass before and after being immersed in a JIS K 6258 immersion test for a non-mineral brake fluid for automobiles specified in JIS K 2233 An on-site molded gasket composition having excellent brake fluid resistance, characterized in that the volume change rate is 50% or less.
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl polymer having two or more groups represented by the formula (1) and having one or more groups represented by the general formula (1) at the molecular end thereof,
(B) Initiator. In the immersion test of JIS K 6258 with respect to the antifreeze liquid defined in JIS K 2234, the mass and volume change rate before and after immersion are 50, which contains the component (A) and the component (B) as essential components. % Composition for on-site molded gaskets having excellent coolant resistance, characterized by being less than or equal to%. The on-site molded gasket composition according to claim 1 or 2, wherein the vinyl monomer constituting the main chain of the component (A) is a (meth) acrylic monomer. The on-site molded gasket composition according to any one of claims 1 to 3, wherein the vinyl monomer constituting the main chain of component (A) is an acrylate monomer. The in-situ molding according to any one of claims 1 to 4, wherein the vinyl monomer constituting the main chain of component (A) contains at least two selected from butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate. Gasket composition. ^Ra in General formula (1) of (A) component is a hydrogen atom or a C1-C20 hydrocarbon group, The composition for in-situ molded gaskets in any one of Claims 1-5. The composition for in-situ molded gasket according to claim 6, wherein R ^a in the general formula (1) of the component (A) is a hydrogen atom or a methyl group. The composition for in-situ molded gaskets according to any one of claims 1 to 7, which is used for sealing a site requiring oil resistance. The composition for in-situ molded gaskets according to any one of claims 1 to 8, which is used for sealing a site requiring heat resistance. The composition for in-situ molded gaskets according to any one of claims 1 and 3 to 9, which is used around a brake of an automobile. The composition for in-situ molded gaskets according to any one of claims 2 to 9, which is used for sealing around a radiator of a liquid-cooled internal combustion engine. The component (A) is
To the vinyl polymer having a halogen group at the end,
General formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The composition for on-site molded gaskets in any one of Claims 1-11 manufactured by making the compound shown by react. A vinyl polymer having a halogen group at the end is represented by the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to the ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
The composition for in-situ molded gaskets of Claim 12 which has group shown by these. The component (A) is
To the vinyl polymer having a hydroxyl group at the end,
General formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The composition for on-site molded gaskets in any one of Claims 1-11 manufactured by making the compound shown by react. The component (A) is
(1) A diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at a terminal,
(2) Residual isocyanate group and general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The composition for in-situ molded gaskets in any one of Claims 1-11 manufactured by making it react with the compound shown by these. The composition for in-situ molded gaskets according to any one of claims 1 to 15, wherein the main chain of the component (A) is produced by living radical polymerization of a vinyl monomer. The composition for in-situ molded gasket according to claim 16, wherein the living radical polymerization is atom transfer radical polymerization. The composition for in-situ molded gasket according to claim 17, wherein the transition metal complex which is a catalyst for atom transfer radical polymerization is selected from a complex of copper, nickel, ruthenium or iron. The composition for in-situ molded gasket according to claim 18, wherein the transition metal complex is a copper complex. The composition for in-situ molded gaskets according to any one of claims 1 to 15, wherein the main chain of the component (A) is produced by polymerization of a vinyl monomer using a chain transfer agent. The number average molecular weight of the said (A) component is 3000 or more, The composition for on-site molded gaskets in any one of Claims 1-20. The site according to any one of claims 1 to 21, wherein the vinyl polymer of the component (A) has a ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is less than 1.8. Composition for molded gaskets. The composition for in-situ molded gasket according to any one of claims 1 to 22, wherein the component (B) is a radical initiator. The composition for on-site molded gasket according to any one of claims 1 to 22, wherein the component (B) is an anionic initiator. The composition for on-site molded gasket according to any one of claims 1 to 22, wherein the component (B) is a redox initiator. The composition for in-situ molded gaskets according to any one of claims 1 to 25, comprising a monomer and / or an oligomer having a radical polymerizable group. The composition for in-situ molded gaskets according to any one of claims 1 to 26, comprising a monomer and / or an oligomer having an anionically polymerizable group. The composition for in situ molding gaskets in any one of Claims 26-27 containing the monomer and / or oligomer which have a (meth) acryloyl type group. 29. The in-situ molded gasket composition according to claim 28, further comprising a monomer and / or an oligomer having a (meth) acryloyl group and a number average molecular weight of 5000 or less. An on-site molded gasket comprising the composition for a curable on-site molded gasket according to any one of claims 1 to 29. An in-situ molded gasket obtained by subjecting the composition for a curable in-situ molded gasket according to any one of claims 1 to 29 to at least one of radical polymerization, anionic polymerization, and oxidation-reduction polymerization.