JP5228882B2 - Sealant composition - Google Patents

Description

  The present invention relates to a sealant composition. More specifically, the present invention relates to a sealing material composition that is easy to manufacture and excellent in curability and cured product characteristics.

  In addition to giving a polymer having a methacryloyl group at the end of the molecular chain by itself or by using a curing catalyst, a monomer, an initiator, etc., giving a cured product having excellent heat resistance and durability, It is known that the curability is fast. Examples of the main chain skeleton of such polymers include polyether polymers such as polyethylene oxide, polypropylene oxide, and polytetramethylene oxide, hydrocarbons such as polybutadiene, polyisoprene, polychloroprene, polyisobutylene, and hydrogenated products thereof. Examples of such polymers include polysiloxane polymers such as polydimethylsiloxane and polydimethylsiloxane, which are used in various applications depending on the characteristics of the main chain skeleton.

  In particular, vinyl polymers have characteristics that cannot be obtained by the above-mentioned various polymers such as high weather resistance, heat resistance, oil resistance and transparency, and the curable composition is proposed to be used in various fields. Has been.

  Patent Document 1 discloses the production of an acrylic polymer having a hydroxyl group at the terminal by using a hydroxyl group-containing sulfide as a chain transfer agent, and further reacting the hydroxyl group to produce an acrylic polymer having a methacryloyl group at the terminal. ing.

In Patent Document 2, a vinyl polymer having an acryloyl group at the terminal is produced using a living radical polymerization method, an initiator or the like is blended into the obtained vinyl polymer, and photocured. It is disclosed that a rubber-like cured product can be obtained.
JP-A-5-262808 JP 2000-72816 A

  However, in the method produced by general radical polymerization as disclosed in Patent Document 1, it is difficult to reliably introduce an acryloyl group at the end of the polymer. In these methods, since normal radical polymerization is used, the ratio of the obtained weight average molecular weight (hereinafter also referred to as “Mw”) to the number average molecular weight (hereinafter also referred to as “Mn”) (hereinafter referred to as “Mw / Mn”). The molecular weight between cross-linking points could not be controlled, and good cured product characteristics could not be obtained.

  The ATRP (Atom Transfer Radical Polymerization) method disclosed in Patent Document 2 is a method using copper bromide or the like as a catalyst, and it is difficult to remove toxic copper from a vinyl polymer, and the manufacturing process is complicated. Become. Therefore, a great economic burden is required. In addition, there is a problem that a halide such as bromine remains, which adversely affects weather resistance and durability, and a metal such as copper, which also adversely affects insulation.

  The present invention has been made in view of the above-mentioned problems, and its object is to provide a vinyl polymer having a high proportion of (meth) acryloyl groups at the molecular terminals at a low cost and in an easy manner. It is to provide a sealant composition that cures at a high speed and has high cured properties.

  As a result of intensive studies in view of the above problems, the present inventors have found that a composition containing a vinyl polymer produced using a specific living radical polymerization initiator exhibits excellent curability and exhibits high cured product characteristics. I found out. Furthermore, after producing a vinyl polymer having a carboxyl group at the end using a specific living radical polymerization initiator, a methacryloyl group is obtained at the molecular end obtained by reacting the vinyl polymer with a specific glycidyl compound. It has been found that a composition containing a vinyl polymer having a high ratio exhibits excellent curability and exhibits high cured product characteristics, and the present invention has been completed.

  That is, the sealing material composition according to the present invention is a sealing material composition containing a vinyl polymer having at least one (meth) acryloyl group per molecule at the molecular end, wherein the vinyl polymer is A vinyl monomer is produced by living radical polymerization using the compound represented by the general formula (1) as a polymerization initiator.

〔式中、Ｒ¹は水素原子又は炭素数１〜２のアルキル基であり、Ｒ²は炭素数１〜２のアルキル基又はニトリル基であり、Ｒ³は−（ＣＨ₂）ｍ−（ｍは０〜２の整数である。）であり、Ｒ⁴及びＲ⁵は互いに独立して炭素数１〜４のアルキル基である。〕

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ² represents an alkyl group or nitrile group having 1 to ² carbon atoms, and R ³ represents — (CH ₂ ) m — (m R ⁴ and R ⁵ are each independently an alkyl group having 1 to 4 carbon atoms. ]

  The vinyl polymer is preferably a (meth) acrylic polymer.

  The number average molecular weight of the vinyl polymer is preferably 3000 to 50000.

  The vinyl polymer preferably has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) of less than 2.0.

  The vinyl polymer has a carboxyl group at the terminal by living radical polymerization of a vinyl monomer containing a carboxyl group represented by the general formula (2) using the compound represented by the general formula (1) as a living radical polymerization initiator. It is preferable that the vinyl polymer is produced by producing a vinyl polymer having a group and reacting the vinyl polymer with a glycidyl compound having a methacryloyl group represented by the general formula (3). .

〔式中、Ｒ⁶は水素原子又はメチル基であり、Ｒ⁷はあってもなくてもよく、Ｒ⁷を有する場合は、−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−又は−Ｃ₆Ｈ₄−であり、Ｒ⁸はＲ⁹−Ｏ−（Ｒ⁹は炭素数２〜４のアルキル基）、Ｒ¹⁰−Ｃ（Ｏ）−Ｏ−（Ｒ¹⁰は炭素数１〜８のアルキル基）、Ｒ¹¹−Ｏ−Ｃ（Ｏ）−Ｒ¹²−（Ｒ¹¹は炭素数１〜８のアルキル基、Ｒ¹²は炭素数１〜８のアルキル基）、−Ｃ₆Ｈ₄−又は−ＣＨ₂＝ＣＨ₂−であり、ｎは０〜４である。〕

Wherein, R ⁶ is a hydrogen atom or a methyl group, it may or may not be R ⁷ is a, if having R ⁷ is, -C (O) -O -, - OC (O) -, - NH— or —C ₆ H ₄ —, R ⁸ is R ⁹ —O— (R ⁹ is an alkyl group having 2 to 4 carbon atoms), R ¹⁰ —C (O) —O— (R ¹⁰ is carbon number) 1-8 alkyl group), R ¹¹ —O—C (O) —R ¹² — (R ¹¹ is an alkyl group having 1 to 8 carbon atoms, R ¹² is an alkyl group having 1 to 8 carbon atoms), —C ₆ H ₄ — or —CH ₂ ═CH ₂ —, and n is 0 to 4. ]

〔式中、Ｒ¹³は水素原子又はメチル基であり、Ｒ¹⁴はあってもなくてもよく、Ｒ¹⁴を有する場合は、−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−又は−Ｃ₆Ｈ₄−であり、
Ｒ¹⁵はＲ¹⁶−Ｏ−（Ｒ¹⁶は炭素数２〜４のアルキル基）、Ｒ¹⁷−Ｃ（Ｏ）−Ｏ−（Ｒ¹⁷は炭素数１〜８のアルキル基）、Ｒ¹⁸−Ｏ−Ｃ（Ｏ）−Ｒ¹⁹−（Ｒ¹⁸は炭素数１〜８のアルキル基、Ｒ¹⁹は炭素数１〜８のアルキル基）、−Ｃ₆Ｈ₄−又は−ＣＨ₂＝ＣＨ₂−であり、ｎは０〜４である。〕

Wherein, R ¹³ is a hydrogen atom or a methyl group, may or may not be R ¹⁴ is a, if having a R ¹⁴ are, -C (O) -O -, - OC (O) -, - NH— or —C ₆ H ₄ —,
R ¹⁵ is R ¹⁶ —O— (R ¹⁶ is an alkyl group having 2 to 4 carbon atoms), R ¹⁷ —C (O) —O— (R ¹⁷ is an alkyl group having 1 to 8 carbon atoms), R ¹⁸ —O —C (O) —R ¹⁹ — (R ¹⁸ is an alkyl group having 1 to 8 carbon atoms, R ¹⁹ is an alkyl group having 1 to 8 carbon atoms), —C ₆ H ₄ — or —CH ₂ ═CH ₂ —. Yes, n is 0-4. ]

  As described above, the sealing material composition according to the present invention includes a vinyl polymer having at least one (meth) acryloyl group produced at a molecular end, produced using a specific living radical polymerization initiator. Therefore, it has excellent copolymerizability with vinyl monomers and fast curability, and the obtained cured product exhibits excellent mechanical properties, high weather resistance and heat resistance. Further, the vinyl polymer having at least one methacryloyl group can be easily and inexpensively produced by the method for producing a vinyl polymer of the present invention.

  The living radical polymerization method used in the present invention is a living radical polymerization method using a nitrooxide radical disclosed in JP-T-2003-500378 and can polymerize various vinyl monomers with good control. In this method, a vinyl monomer is polymerized using a specific polymerization initiator represented by the general formula (1), and a carboxyl group, glycidyl group, hydroxyl group or isocyanate group represented by the general formulas (2) to (5). A vinyl polymer having a carboxyl group, a glycidyl group, a hydroxyl group, or an isocyanate group at the terminal can be obtained by block copolymerization of a vinyl monomer having a. Specifically, the vinyl polymer according to the present invention can be obtained by the following steps.

[1] Vinyl having a carboxyl group at the terminal by living radical polymerization of a vinyl monomer containing a carboxyl group represented by the general formula (2) using the compound represented by the general formula (1) as a living radical polymerization initiator A polymer is produced, and the vinyl polymer is reacted with a glycidyl compound having a methacryloyl group represented by the general formula (3).

[2] A vinyl having a glycidyl group at its terminal by living radical polymerization of a vinyl monomer containing a glycidyl compound represented by the general formula (3) using the compound represented by the general formula (1) as a living radical polymerization initiator A polymer is produced, and the vinyl polymer is reacted with a carboxyl compound having a methacryloyl group represented by the general formula (2).

[3] Vinyl having a hydroxy group at the terminal by living radical polymerization of a vinyl monomer containing a hydroxy group represented by general formula (4) using the compound represented by general formula (1) as a living radical polymerization initiator A polymer is produced, and the vinyl polymer is reacted with an isocyanate compound having a methacryloyl group represented by the general formula (5).

[4] Vinyl having an isocyanate group at the terminal end by living radical polymerization of a vinyl monomer containing an isocyanate group represented by the general formula (5) using the compound represented by the general formula (1) as a living radical polymerization initiator. A polymer is produced, and the vinyl polymer is reacted with a hydroxy compound having a methacryloyl group represented by the general formula (4).

〔式中、Ｒ²⁰は水素原子又はメチル基であり、Ｒ²¹はあってもなくてもよく、Ｒ²¹を有する場合は、−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−又は−Ｃ₆Ｈ₄−であり、
Ｒ²²はＲ²³−Ｏ−（Ｒ²³は炭素数２〜４のアルキル基）、Ｒ²⁴−Ｃ（Ｏ）−Ｏ−（Ｒ²⁴は炭素数１〜８のアルキル基）、Ｒ²⁵−Ｏ−Ｃ（Ｏ）−Ｒ²⁶−（Ｒ²⁵は炭素数１〜８のアルキル基、Ｒ²⁶は炭素数１〜８のアルキル基）、−Ｃ₆Ｈ₄−又は−ＣＨ₂＝ＣＨ₂−であり、ｎは０〜４である。〕

Wherein, R ²⁰ is a hydrogen atom or a methyl group, may or may not be R ²¹ is a, if having a R ²¹ are, -C (O) -O -, - OC (O) -, - NH— or —C ₆ H ₄ —,
R ²² is R ²³ —O— (R ²³ is an alkyl group having 2 to 4 carbon atoms), R ²⁴ —C (O) —O— (R ²⁴ is an alkyl group having 1 to 8 carbon atoms), R ²⁵ —O —C (O) —R ²⁶ — (R ²⁵ is an alkyl group having 1 to 8 carbon atoms, R ²⁶ is an alkyl group having 1 to 8 carbon atoms), —C ₆ H ₄ — or —CH ₂ ═CH ₂ —. Yes, n is 0-4. ]

〔式中、Ｒ²⁷は水素原子又はメチル基であり、Ｒ²⁸はあってもなくてもよく、Ｒ²⁸を有する場合は、−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−又は−Ｃ₆Ｈ₄−であり、
Ｒ²⁹はＲ³⁰−Ｏ−（Ｒ³⁰は炭素数２〜４のアルキル基）、Ｒ³¹−Ｃ（Ｏ）−Ｏ−（Ｒ³¹は炭素数１〜８のアルキル基）、Ｒ³²−Ｏ−Ｃ（Ｏ）−Ｒ³³−（Ｒ³²は炭素数１〜８のアルキル基、Ｒ³³は炭素数１〜８のアルキル基）、−Ｃ₆Ｈ₄−又は−ＣＨ₂＝ＣＨ₂−であり、ｎは０〜４である。〕

Wherein, R ²⁷ is a hydrogen atom or a methyl group, may or may not be R ²⁸ is a, if having a R ²⁸ are, -C (O) -O -, - OC (O) -, - NH— or —C ₆ H ₄ —,
R ²⁹ is R ³⁰ —O— (R ³⁰ is an alkyl group having 2 to 4 carbon atoms), R ³¹ —C (O) —O— (R ³¹ is an alkyl group having 1 to 8 carbon atoms), R ³² —O —C (O) —R ³³ — (R ³² is an alkyl group having 1 to 8 carbon atoms, R ³³ is an alkyl group having 1 to 8 carbon atoms), —C ₆ H ₄ — or —CH ₂ ═CH ₂ —. Yes, n is 0-4. ]

  In the above step [1], the molar ratio between the vinyl polymer having a carboxyl group at the terminal and the glycidyl compound having a methacryloyl group represented by the general formula (3) is 1: 0.8 to 2.0. Preferably there is.

  In the above step [2], the molar ratio of the vinyl polymer having a glycidyl group at the terminal and the carboxyl compound having a methacryloyl group represented by the general formula (2) is 1: 0.8 to 2.0. It is preferable.

  In the above step [3], the molar ratio of the vinyl polymer having a hydroxyl group at the terminal and the isocyanate compound having a methacryloyl group represented by the general formula (5) is 1: 0.8 to 2.0. It is preferable.

  In the above step [4], the molar ratio of the vinyl polymer having an isocyanate group at the terminal and the hydroxy compound having a methacryloyl group represented by the general formula (4) is 1: 0.8 to 2.0. It is preferable.

  When the compound having a methacryloyl group with respect to each of the vinyl polymers 1 is less than 0.8 mol, there is a polymer chain having no methacryloyl group introduced at the terminal, which causes poor curing. It becomes. Moreover, when the compound which has a methacryloyl group with respect to each said vinyl polymer 1 is larger than 2 mol, many compounds which have a methacryloyl group remain, and storage stability worsens.

  The living radical polymerization used in the present invention can be polymerized by any process such as batch process, semi-batch process, tubular continuous polymerization process, and continuous stirred tank process (CSTR). Among these polymerization processes, batch processes, semi-batch processes and tubular continuous polymerization processes are preferable, and batch processes are particularly preferable. The polymerization method may be bulk polymerization without using a solvent, or solvent-based solution polymerization.

  The polymerization temperature is preferably 100 to 150 ° C, more preferably 105 ° C to 135 ° C, and particularly preferably 110 to 125 ° C. When the polymerization temperature is less than 100 ° C., the polymerization rate is remarkably slowed. On the other hand, when the polymerization temperature is higher than 150 ° C., the nitrooxide radical cannot cap the growing radical, and the recombination reaction or disproportionation reaction between the growing radicals, or the hydrogen abstraction reaction or back-biting reaction from the polymer main chain. Β-decomposition reaction occurs, the living polymerizability is lost, and radical polymerization cannot be controlled.

  The polymerization solvent used in the present invention is preferably an organic hydrocarbon compound. Specifically, cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and orthoformate Alcohols such as methyl, methyl orthoacetate, methanol, ethanol and isopropanol are exemplified, and one or more of these can be used.

  0-200 mass parts is preferable with respect to 100 mass parts of vinyl-type monomers, and, as for the usage-amount of a solvent, it is more preferable to set it as 0-100 mass parts. Especially preferably, it is 0-50 mass parts. When there is too much solvent, chain transfer reaction resulting from a solvent will generate | occur | produce and superposition | polymerization control, such as molecular weight control, molecular weight distribution control, and the living property of a terminal, will worsen.

  The vinyl monomer used in the polymerization of the present invention is not particularly limited as long as it has radical polymerizability, and various types can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid-3-methoxypropyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) 2-aminoethyl acrylate, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid-2-perfluoro Ethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethyl (meth) acrylate Methyl, (meth) acrylic acid 2-perfluoromethyl-2-perful (Meth) acrylic acid monomers such as roethylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate; styrene, Styrenic monomers such as vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; maleic anhydride, maleic acid, maleic acid Monoalkyl and dialkyl esters of fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octyl Maleimide monomers such as maleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate and propion Vinyl esters such as vinyl acid vinyl, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, etc. Can be mentioned. These may be used alone or a plurality of these may be copolymerized. In the above expression format, for example, (meth) acrylic acid represents acrylic acid or methacrylic acid.

  The vinyl-type monomer which has a carboxyl group copolymerized by living radical polymerization in this invention is shown by General formula (2). Specific examples include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene.

  The vinyl-type monomer which has a glycidyl group copolymerized by living radical polymerization in this invention is shown by General formula (3). Specific examples include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate.

  The vinyl-type monomer which has a hydroxyl group copolymerized by living radical polymerization in this invention is shown by General formula (4). Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate And hydroxyalkyl (meth) acrylates such as pentaerythritol tri, di or mono (meth) acrylate and trimethylolpropane di or mono (meth) acrylate.

  The vinyl monomer having an isocyanate group copolymerized by living radical polymerization in the present invention is represented by the general formula (5). Specific examples include 2-ethyl isocyanate (meth) acrylate and isocyanate (meth) acrylate.

  The vinyl monomer having a carboxyl group may be added to the polymerization system from the beginning, but is preferably added to the polymerization system when the polymerization rate is 70% to 99%. More preferably, the polymerization rate is 85% to 98%, and particularly preferably 93% to 97%. When added at a polymerization rate of less than 70%, it becomes close to the α-terminal carboxyl group and the molecular weight between the crosslinking points is shortened, so that excellent mechanical properties and the like cannot be obtained. On the other hand, if the polymerization rate exceeds 99%, the copolymerization rate decreases, and there is a possibility that it will not be introduced into the polymer chain.

  Moreover, when adding the vinyl-type monomer of General formula (2)-(5) which carries out the block copolymerization, you may add another vinyl-type monomer simultaneously.

  Reaction of a vinyl polymer having a carboxyl group, glycidyl group, hydroxyl group or isocyanate group with a methacryl monomer having a glycidyl group, carboxyl group, isocyanate group or hydroxyl group represented by the general formulas (2) to (5) The temperature is preferably 40 to 110 ° C. More preferably, it is 50-100 degreeC, Most preferably, it is 60-90 degreeC. When it is lower than 40 ° C., the reaction is slow and production efficiency is remarkably deteriorated. On the other hand, when the reaction temperature is higher than 90 ° C., the methacryloyl group may be added to the vinyl polymer.

  In the above reaction, it is preferable to use a catalyst in order to increase production efficiency. The catalyst is not particularly limited as long as it accelerates these reactions and does not affect the methacryloyl group. As a catalyst for the reaction between the carboxyl group and the glycidyl group, tributylammonium bromide is preferable. Tributylammonium bromide does not affect the reaction of the methacryloyl group, and can effectively accelerate the reaction between the carboxyl group and the glycidyl group. In addition, as a catalyst for the reaction of hydroxyl group and isocyanate group, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetoacetonate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethyl maleate Dibutyltin dibutyl malate, dibutyltin diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethyl And tetravalent tin compounds such as malate and dioctyltin diisooctylmalate.

  The addition amount of the catalyst is preferably 0.1 to 2% by mass, more preferably 0.2 to 1% by mass with respect to the amount of the (meth) acrylic polymer having a carboxyl group at the terminal, and 0 It is particularly preferably 3 to 0.5% by mass. When the amount of the catalyst is less than 0.1% by mass, the effect is small and the productivity cannot be improved. On the other hand, when the amount of the catalyst exceeds 2% by mass, there is an adverse effect such as precipitation in the subsequent product.

  The molecular weight of the vinyl polymer having at least one methacryloyl group produced in the present invention at the molecular end is 3000 to 50000 in terms of number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC). It is preferable. More preferably, it is 6000-25000. When Mn is lower than 3000, the crosslink density of the cured product becomes too high, and the elongation of the cured product becomes extremely small. When Mn is higher than 50000, the viscosity becomes very high and workability is remarkably deteriorated. Although there is no restriction | limiting in particular in molecular weight distribution (Mw / Mn), Less than 2.0 (usually 1.05 or more) is preferable. More preferably, it is 1.3-1.8.

The number f of methacryloyl groups per polymer chain is preferably 1.0 to 10.0. The number is more preferably 1.4 to 4.0, and particularly preferably 1.8 to 3.5. f is calculated as follows.
f = Concentration of methacryloyl group in polymer [mol / kg] / (1000 / number average molecular weight)
When f is smaller than 1.0, the cured product has a low crosslink density, so that the breaking strength is very weak. On the other hand, when the number is more than 10.0, the crosslink density is too high, and the cured product is brittle and does not stretch.

  The vinyl polymer having at least one (meth) acryloyl group at the molecular end produced in the present invention may require a step of removing residual volatiles after the reaction. Any demelting process may be used as long as it is a commonly used demelting process such as a falling evaporator, a thin film evaporator or an extruder dryer. The demelting temperature condition is preferably 250 ° C. or lower. More preferably, it is 170 degrees C or less, Most preferably, it is 100 degrees C or less. If it is 250 degrees C or less, a living radical polymerization terminal will not dissociate and the production | generation of the low molecular weight substance by decomposition | disassembly of a polymer will not occur. On the other hand, when it exceeds 250 ° C., the living polymerization terminal is dissociated, and the polymer chain is partially decomposed to produce a low molecular weight product. Moreover, since coloring also occurs, it is not preferable.

  Although the sealing material composition of this invention is not specifically limited, It is preferable to harden | cure by active energy rays, such as an ultraviolet-ray, visible light, and an electron beam, or a heat | fever. A suitable polymerization initiator is used for each curing method.

When curing with active energy rays, it is preferable to contain a photopolymerization initiator. Although there is no restriction | limiting in particular as a photoinitiator, A photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is especially preferable. Specifically, benzoin such as benzoin, benzoin methyl ether and benzoin propyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2 -Hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and N , Acetophenone such as N-dimethylaminoacetophenone; anthraquinone such as 2-methylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxa And thioxanthones such as 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzylmethyl ketal; benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone and 4-benzoyl Benzophenones such as -4'-methyldiphenyl sulfide; and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4'-trimethylpentylphosphine oxide, camphorquinone, etc. Can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more. Furthermore, you may combine with sensitizers, such as amines.

  The addition amount of the photopolymerization initiator is not particularly limited since it only needs to slightly functionalize the system, but is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the vinyl polymer. More preferably, it is 0.1-30 mass parts, More preferably, it is 0.5-10 mass parts. The active energy ray source is not particularly limited, but depending on the nature of the photopolymerization initiator, for example, irradiation of light and electron beam by a high pressure mercury lamp, low pressure mercury lamp, electron beam irradiation device, halogen lamp, light emitting diode, semiconductor laser, etc. Is mentioned.

  When curing by heat, it is preferable to contain a thermal polymerization initiator. Although it does not specifically limit as a thermal-polymerization initiator, An azo initiator, a peroxide, a persulfate, and a redox initiator are contained. Suitable azo initiators include, but are not limited to, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) 2 Hydrochloride, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), 2,2'-azobis-2-methylbutyronitrile, 1,1- Azobis (1-cyclohexanecarbonitrile), 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (methylisobutyrate) and the like can be mentioned. Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, t-butyl peroxyisopropyl monocarbonate, Di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, and dicumyl peroxide Etc. Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, and ammonium persulfate. Suitable redox (oxidation) initiators include, but are not limited to, combinations of the above-described persulfate initiators with reducing agents such as sodium metabisulfite and sodium bisulfite; Examples include systems based on tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate. Other initiators include, but are not limited to, pinacol such as tetraphenyl 1,1,2,2-ethanediol. As the thermal polymerization initiator, one selected from the group consisting of an azo initiator and a peroxide initiator is preferable. These photopolymerization initiators may be used alone or in combination of two or more.

  The thermal polymerization initiator used in the present invention is present in a catalytically effective amount, and such amount is not limited, but is typically 0.01 to 100 parts by mass of the vinyl polymer. -50 mass parts is preferable. More preferably, it is 0.1-20 mass parts, More preferably, it is 0.5-10 mass parts.

  The thermosetting conditions are not particularly limited, but the temperature varies depending on the type of the thermal polymerization initiator, polymer, compound to be added, etc., but is preferably in the range of 50 ° C to 250 ° C, 70 ° C to 200 ° C. The range of is more preferable. The curing time varies depending on the polymerization initiator, monomer, solvent, reaction temperature, etc., but is usually in the range of 1 minute to 24 hours.

  The sealing material composition of the present invention may contain a polymerizable monomer and / or oligomer depending on the purpose. 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, (Meth) acrylic acid 2-perfluorohexadecylethyl, isobornyl acrylate and the like.

  Examples of the styrenic monomer include styrene and α-methylstyrene. Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the acrylamide monomer 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.

  Examples of oligomers include bisphenol A type epoxy acrylate resins, phenol novolac type epoxy acrylate resins, cresol novolac type epoxy acrylate resins, carboxyl group-modified epoxy acrylate type resins, and the like; polyols (polytetramethylene glycol, ethylene glycol and adipine Acid polyester diol, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanate (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane) Diisocyanate, hexamethylene dii A urethane resin obtained from cyanate, xylylene diisocyanate, etc.) with a hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.} Urethane acrylate resin obtained by reaction; resin 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.

  Of 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.

  Although there is no restriction | limiting in particular as a compounding quantity of a polymerizable monomer and / or oligomer, It is preferable that it is 1-200 mass parts with respect to 100 mass parts of vinyl polymers, and it is more preferable that it is 5-100 mass parts. 10 to 50 parts by mass is particularly preferable. A blending amount within the above range is preferable because the viscosity of the sealing material composition is low, curability is good, and cured product characteristics are excellent.

The sealing material composition of the present invention may further contain reinforcing silica. Examples of the reinforcing silica include fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid and the like. 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. Among them, the specific surface area (according to BET adsorption method) of 50 m ² / g or more, usually 50 to 400 m ² / g, is preferably 100 to 300 m ² / g approximately ultrafine powdery silica preferred. Further, surface-treated silica, for example, surface-treated with an organosilicon compound such as organosilane, organosilazane, diorganocyclopolysiloxane and the like is more preferable because it is easy to develop fluidity suitable for molding. More specific examples of the reinforcing silica system include, but are not particularly limited to, Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Sil, Ltd., Nippon Silica Co., Ltd., which is one of the precipitated silicas. It is done.

  Although there is no restriction | limiting in particular as addition amount of this reinforcing silica, 0.1-100 mass parts with respect to 100 mass parts of vinyl polymers, Preferably it is 0.5-80 mass parts, Especially 1-50 mass parts. It is preferable to use it. When the blending amount is less than 0.1 parts by mass, the effect of improving the reinforcing property may not be sufficient, and when it exceeds 100 parts by mass, the workability of the sealing material composition may be deteriorated. The reinforcing silica of the present invention may be used alone or in combination of two or more.

  In the sealing material composition of the present invention, various additives for adjusting physical properties, for example, flame retardants, anti-aging agents, fillers, plasticizers, curable modifiers, physical property modifiers, adhesion imparting agents, A storage stability improver, a solvent, a radical inhibitor, a metal deactivator, an ozone deterioration inhibitor, a phosphorus peroxide decomposer, a lubricant, a pigment, a foaming agent, and the like may be appropriately blended as necessary. These various additives may be used alone or in combination of two or more. In addition, since the vinyl polymer is originally a polymer having excellent durability, an anti-aging agent is not always necessary, but a conventionally known antioxidant, ultraviolet absorber, light stabilizer and the like may be appropriately used. it can.

  Specific examples of fillers include reinforcing fillers such as fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, Fillers such as talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white and shirasu balloon; fibrous fillers such as asbestos, glass fibers and filaments can be used. When it is desired to obtain a cured product having high strength with these fillers, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activated zinc A preferable result can be obtained by adding a filler selected from flower or the like in a range of 0 to 250 parts by mass with respect to 100 parts by mass of the vinyl polymer. The range of 80-180 mass parts is more preferable. Further, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like is used as the vinyl polymer 100. If it adds in the range of 0-200 mass parts with respect to a mass part, a preferable result will be obtained. A range of 80 to 150 parts by weight is more preferable. These fillers may be used alone or in combination of two or more.

  Specific examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, and butyl benzyl phthalate; Basic acid esters; Esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Polyerylene glycol, polypropylene glycol or hydroxyl groups thereof are converted Polyethers; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; Tg-10 ° C. or less with a weight average molecular weight (Mw) of 1000 to 7000 Poly (meth) acrylate. The amount of the plasticizer is preferably added in the range of 0 to 400 parts by mass with respect to 100 parts by mass of the vinyl polymer, more preferably 0 to 200 parts by mass, and 0 to 100 parts by mass. Particularly preferred.

  As the adhesion-imparting agent, aminosilane, epoxysilane, vinylsilane, methylsilane, or the like may be used.

  Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve, and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. Is mentioned. Those solvents may be used in the production of the polymer.

  Although the sealing material composition which concerns on this invention contains the above components, the manufacturing method is not specifically limited. Specifically, it can be produced by mixing using a stirrer, a planetary stirrer, or the like.

  Since the sealing material composition according to the present invention is excellent in storage stability even at a relatively high temperature, the composition can be handled with a lower viscosity, and is suitable for liquid injection molding at a high temperature. In the present invention, when the sealing material composition is flowed, it is preferably performed at a temperature of 30 ° C. or higher and lower than 80 ° C., but more preferably 40 ° C. or higher and lower than 70 ° C. Moreover, in this invention, while making a sealing material composition flow at the temperature of 30 degreeC or more and less than 80 degreeC, hardening reaction can be performed, making it flow at 30 degreeC or more. That is, the sealing material composition of the present invention can be used as a resin for injection molding (RIM, LIM, etc.).

  A molding method in the case of using the sealing material composition of the present invention as a molded body is not particularly limited, and various commonly used molding methods can be used. For example, cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, thermoforming, and the like can be given. In particular, from the viewpoint of being able to be automated and continuous and being excellent in productivity, the one by injection molding is preferable.

  When the sealing material composition of the present invention is cured as a molded product, it can be removed without substantially damaging the molded product. The fact that the molded body is not substantially damaged means that the molded body has a surface good enough to fulfill its role.

  The sealing material composition of the present invention is not limited, but includes electric / electronic component materials such as solar cell back surface sealing materials, gaskets, casting materials, artificial marble, various molding materials, and meshed glass and laminated glass end faces ( It can be used for various applications such as a sealing material for rust prevention and waterproofing. Furthermore, the molded article showing rubber elasticity obtained from the sealing material composition of the present invention can be widely used mainly for gaskets and packings. For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As an engine component, it can be used as a sealing material for engine oil. In the home appliance field, it can be used for packing, O-rings and the like. Specifically, waterproof packing, insect-proof packing, anti-vibration / sound absorption and air sealing material for cleaner, drip-proof cover for electric water heater, waterproof packing, heater unit packing, electrode unit packing, safety valve diaphragm, waterproof packing, Waterproof packing for solenoid valves, steam microwave ovens and jar rice cookers, water supply tank packing, water absorption valve, water receiving packing, heat insulation heater packing, steam outlet seal, combustion equipment oil packing, O-ring, drain packing, Speaker gaskets, speaker edges, etc. for acoustic equipment such as intake packing, anti-vibration rubber, oil filler packing, oil meter packing, diaphragm valve, etc. In the construction field, it can be used for structural gaskets (zipper gaskets), waterproof materials, and regular sealing materials. In the sports field, it can be used as an all-weather pavement material, gymnasium floor, etc. as a sports floor. In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like. In the marine and civil engineering fields, it can be used for waterstops, tarpaulins, etc. as structural materials.

<Synthesis of vinyl polymer>
Examples of the present invention will be described below together with synthesis examples and comparative examples, but it goes without saying that the scope of the present invention is not limited to these examples. In the following, “part” is based on mass unless otherwise specified.

(Production Method of Polymer A) 341 parts by mass of butyl acrylate (hereinafter also referred to as “BA”), living radical polymerization initiator [formula (6 )] A mixed solution consisting of 17.0 parts by mass and 341 parts by mass of butyl acetate was charged, and the mixed solution was sufficiently deaerated by nitrogen bubbling. The jacket temperature was raised to 112 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 2 hours, the polymerization rate of BA was 74%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 220 parts by mass of a polymer. The properties of the obtained polymer were Mw8600, Mn6230, Mw / Mn1.38. Next, in a 1 liter pressurized stirring layer reactor equipped with an oil jacket, 215 parts by mass of PBA polymer, 45 parts by mass of BA, 6 parts by mass of methacrylic acid (hereinafter also referred to as “MAA”), 221 parts by mass of butyl acetate. The mixed solution consisting of was thoroughly degassed by nitrogen bubbling. The jacket temperature was raised to 112 ° C., the polymerization reaction was started, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 6 hours, the polymerization rate of BA was 96%, and the polymerization rate of MAA was 98%. The reaction liquid temperature is cooled to 85 ° C., and 23 parts by mass of 4-hydroxybutyl acrylate glycidyl ether (hereinafter also referred to as “4HBAGE”) and 9 parts by mass of tetrabutylammonium bromide (hereinafter also referred to as “TBAB”) are added thereto. The reaction was continued for 8 hours at 85 ° C. At this time, the reaction rate of 4HBAGE was 97%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 220 parts by mass of a polymer. The properties of the polymer were Mw13150, Mn7460, Mw / Mn1.76, E-type viscosity (25 ° C.) 68900 mPa · s. The number f of acryloyl groups per one polymer chain of the polymer was 2.6.

(Production Method of Polymer B) In a 1 liter pressurized stirred layer reactor equipped with an oil jacket, BA348 parts by mass, living radical polymerization initiator [Formula (6)] 4.1 parts by mass, butyl acetate 348 parts by mass A mixed solution consisting of parts was charged, and the mixed solution was sufficiently deaerated by nitrogen bubbling. The jacket temperature was raised to 112 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 3 hours, the polymerization rate of BA was 71%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 220 parts by mass of a polymer. The properties of the obtained polymer were Mw26280, Mn18910, Mw / Mn1.39. Next, a mixed liquid composed of 212 parts by mass of PBA polymer, 14 parts by mass of BA, 2 parts by mass of MAA, and 220 parts by mass of butyl acetate was charged into a 1 liter pressurized stirred layer reactor equipped with an oil jacket. It was fully deaerated by bubbling. The jacket temperature was raised to 112 ° C., the polymerization reaction was started, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 6 hours, the polymerization rate of BA was 81%, and the polymerization rate of MAA was 99%. The reaction liquid temperature was cooled to 85 ° C., 6.8 parts by mass of 4HBAGE and 2.7 parts by mass of TBAB were added thereto, and the mixture was reacted at 85 ° C. for 8 hours. At this time, the reaction rate of 4HBAGE was 96%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 220 parts by mass of a polymer. The properties of the polymer were Mw30500, Mn18150, Mw / Mn1.81, and E-type viscosity (25 ° C.) 132500 mPa · s. The number f of acryloyl groups per one polymer chain of the polymer was 2.6.

(Method for Producing Polymer C) In a pressurized stirring layer reactor having a capacity of 1 liter equipped with an oil jacket, 153 parts by mass of BA, 152 parts by mass of ethyl acrylate (hereinafter also referred to as “EA”), ethyl acrylate-2 -A mixed liquid consisting of 35 parts by mass of methoxy (hereinafter also referred to as “C1”), 20.6 parts by mass of a living radical polymerization initiator [Formula (6)], and 240 parts by mass of butyl acetate, was mixed by nitrogen bubbling. Fully evacuated. The jacket temperature was raised to 112 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 1.5 hours, the polymerization rate of BA was 81%, the polymerization rate of EA was 84%, and the polymerization rate of C1 was 82%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 320 parts by mass of a polymer. The properties of the obtained polymer were Mw 7360, Mn 5400, and Mw / Mn 1.36. Next, 241 parts by mass of the polymer, 63 parts by mass of butyl methacrylate (hereinafter also referred to as “BMA”), 8 parts by mass of MAA, and 265 parts by mass of butyl acetate were added to a 1 liter pressurized stirred layer reactor equipped with an oil jacket. The mixed solution consisting of was thoroughly degassed by nitrogen bubbling. The jacket temperature was raised to 112 ° C., the polymerization reaction was started, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 6 hours, the polymerization rate of BMA was 88%, and the polymerization rate of MAA was 87%. The reaction liquid temperature was cooled to 85 ° C., and 39.5 parts by mass of 4HBAGE and 11.6 parts by mass of TBAB were added thereto, and reacted for 8 hours while maintaining at 85 ° C. At this time, the reaction rate of 4HBAGE was 96%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 220 parts by mass of a polymer. The properties of the polymer are Mw12710, Mn7570, Mw / Mn1.68, E-type viscosity (25 ° C.) 241700 mPa · s, and the composition of the polymer is BA / EA / C1 = 43/47/10 (wt) (calculated by NMR) Met. The number f of acryloyl groups per one polymer chain of the polymer was 3.0.

(Manufacturing method of polymer D) BA1159 mass parts, EA157 mass parts, C1 37 mass parts, living radical polymerization initiator [Formula (6)] 5 in a 1 liter pressurized stirring layer reactor equipped with an oil jacket A mixed solution composed of 4 parts by mass and 240 parts by mass of butyl acetate was charged, and the mixed solution was sufficiently deaerated by nitrogen bubbling. The jacket temperature was raised to 112 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 5 hours, the polymerization rate of BA was 84%, the polymerization rate of EA was 86%, and the polymerization rate of C1 was 85%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 320 parts by mass of a polymer. The properties of the obtained polymer were Mw25300, Mn19320, and Mw / Mn1.31. Next, a mixed solution composed of 260 parts by mass of a polymer, 19 parts by mass of BMA, 2.3 parts by mass of MAA, and 290 parts by mass of butyl acetate was charged into a 1 liter pressurized stirring layer reactor equipped with an oil jacket. Full deaeration with nitrogen bubbling. The jacket temperature was raised to 112 ° C., the polymerization reaction was started, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 6 hours, the polymerization rate of BMA was 69%, and the polymerization rate of MAA was 66%. The reaction liquid temperature was cooled to 85 ° C., 8.9 parts by mass of 4HBAGE and 3.5 parts by mass of TBAB were added thereto, and the mixture was reacted at 85 ° C. for 8 hours. At this time, the reaction rate of 4HBAGE was 96%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 220 parts by mass of a polymer. The properties of the polymer are Mw 28420, Mn 19380, Mw / Mn 1.47, E-type viscosity (25 ° C.) 295400 mPa · s, and the composition of the polymer is BA / EA / C1 = 44/47/9 (wt) (calculated by NMR) Met. The number f of acryloyl groups per one polymer chain of the polymer was 3.0.

(Production Method of Polymer E) BA 341 parts by mass, living radical polymerization initiator [Formula (6)] 17.0 parts by mass, butyl acetate 341 parts by mass in a 1 liter pressurized stirring layer reactor equipped with an oil jacket A mixed solution consisting of parts was charged, and the mixed solution was sufficiently deaerated by nitrogen bubbling. The jacket temperature was raised to 112 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 2 hours, the polymerization rate of BA was 74%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 220 parts by mass of a polymer. The properties of the obtained polymer were Mw8600, Mn6230, Mw / Mn1.38. Next, a mixed liquid composed of 191 parts by mass of polymer, 44 parts by mass of BMA, 5 parts by mass of MAA, and 160 parts by mass of butyl acetate was charged into a 1 liter pressurized stirred layer reactor equipped with an oil jacket. It was fully deaerated by bubbling. The jacket temperature was raised to 112 ° C., the polymerization reaction was started, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 6 hours, the polymerization rate of BMA was 71%, and the polymerization rate of MAA was 75%. The reaction solution temperature was cooled to 85 ° C., 16 parts by mass of glycidyl methacrylate (hereinafter also referred to as “GMA”) and 9 parts by mass of TBAB were added thereto, and the reaction was continued for 8 hours at 85 ° C. At this time, the reaction rate of GMA was 99%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at 0.3 kPa and 80 ° C. for 5 hours to obtain about 220 parts by mass of a polymer. The properties of the polymer were Mw12090, Mn7760, Mw / Mn1.56, E-type viscosity (25 ° C.) 66000 mPa · s. The number f of acryloyl groups per one polymer chain of the polymer was 2.8.

(Production Method of Polymer F) Living radical polymerization initiator [Formula (6)] 9.3 parts by mass, 1,6-hexanediol diacrylate (hereinafter also referred to as “HDDA”) 2 in a 1 liter separable flask. A mixed solution consisting of 0.7 parts by mass and 28 parts by mass of ethanol was charged and reacted at 75 ° C. for 2 hours. After the reaction, ethanol was removed from the system by reducing the pressure with a vacuum pump. A mixed liquid consisting of 156 parts by mass of BA, 3.8 parts by mass of 2-ethylhexyl glycidyl ether (hereinafter also referred to as “EHGE”), 4.2 parts by mass of TBAB, and 67 parts by mass of butyl acetate was charged at 112 ° C. for 6 hours. Reacted. At this time, the polymerization rate of BA was 61%, and the reaction rate of EHGE was 92%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 152 parts by mass of a polymer. The properties of the polymer were Mw109890, Mn8370, Mw / Mn1.31. Next, a mixed solution composed of 150 parts by mass of polymer, 51 parts by mass of BMA, 10.2 parts by mass of GMA, and 138 parts by mass of butyl acetate was charged into a 1 liter flask, and the mixed solution was sufficiently deaerated by nitrogen bubbling. The jacket temperature was raised to 112 ° C., the polymerization reaction was started, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 6 hours, the polymerization rate of BMA was 72%, and the polymerization rate of MAA was 78%. The reaction liquid temperature was cooled to 85 ° C., 5.2 parts by mass of acrylic acid (hereinafter also referred to as “AA”) was added thereto, and the mixture was reacted at 85 ° C. for 8 hours. At this time, the reaction rate of AA was 99%. After cooling, the reaction solution was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 140 parts by mass of a polymer. The properties of the polymer were Mw13400, Mn8100, Mw / Mn1.65, E-type viscosity (25 ° C.) 84000 mPa · s. The number f of acryloyl groups per one polymer chain of the polymer was 2.5.

(Production Method of Polymer G) BA 396 parts by mass, living radical polymerization initiator [Formula (6)] 11.8 parts by mass, EHGE 4.8 parts by mass in a 1 liter pressurized stirring layer reactor equipped with an oil jacket Part, TBAB 5.4 parts by mass and butyl acetate 170 parts by mass were charged, and the mixture was sufficiently deaerated by nitrogen bubbling. The jacket temperature was raised to 112 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 6 hours, the polymerization rate of BA was 84%. Thereto was added 4.0 parts by mass of 2-hydroxyethyl methacrylate (hereinafter also referred to as “HEMA”), and the mixture was reacted at 112 ° C. for 6 hours. At this time, the polymerization rate of BA was 95%, and the polymerization rate of HEMA was 93%. The reaction liquid temperature was cooled to 85 ° C., 8.7 parts by mass of 2-ethylisocyanate acrylate (hereinafter also referred to as “AOI”) was added thereto, and the mixture was reacted at 85 ° C. for 8 hours. At this time, the reaction rate of AOI was 96%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 380 parts by mass of a polymer. The properties of the polymer were Mw15300, Mn10200, Mw / Mn1.50, E-type viscosity (25 ° C.) 201000 mPa · s. The number f of acryloyl groups per one polymer chain of the polymer was 1.7.

(Production Method of Polymer H) BA 341 parts by mass, living radical polymerization initiator [Formula (7)] 18.6 parts by mass, butyl acetate 341 parts by mass in a 1 liter pressurized stirring layer reactor equipped with an oil jacket A mixed solution consisting of parts was charged, and the mixed solution was sufficiently deaerated by nitrogen bubbling. The jacket temperature was raised to 112 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 2 hours, the polymerization rate of BA was 70%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 210 parts by mass of a polymer. The properties of the obtained polymer were Mw8000, Mn5900, and Mw / Mn1.36. Next, a mixed liquid composed of 215 parts by mass of PBA polymer, 45 parts by mass of BA, 6 parts by mass of MAA, and 221 parts by mass of butyl acetate was charged into a 1 liter pressurized stirred layer reactor equipped with an oil jacket. It was fully deaerated by bubbling. The jacket temperature was raised to 112 ° C., the polymerization reaction was started, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 112 ° C. After 6 hours, the polymerization rate of BA was 90%, and the polymerization rate of MAA was 92%. The reaction liquid temperature was cooled to 85 ° C., and 22 parts by mass of 4HBAGE and 8 parts by mass of TBAB were added thereto, and the reaction was continued for 8 hours at 85 ° C. At this time, the reaction rate of 4HBAGE was 99%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 210 parts by mass of a polymer. The properties of the polymer were Mw 13250, Mn 7290, Mw / Mn 1.82, and E-type viscosity (25 ° C.) 70020 mPa · s. The number f of acryloyl groups per one polymer chain of the polymer was 2.6.

(Production Method of Polymer I) A 2 liter pressurized stirred layer reactor equipped with an oil jacket was charged with a mixed liquid consisting of 49 parts by mass of BA and 500 parts by mass of butyl acetate, and the mixed liquid was sufficiently desorbed by nitrogen bubbling. I was worried. Subsequently, 0.65 parts by mass of azobisisovaleronitrile (hereinafter also referred to as “AIVN”) is added as a polymerization initiator to start polymerization, and subsequently, BA 530 parts by mass, AA 8.1 parts by mass, and AIVN 6.5 parts by mass. A mixed solution consisting of 150 parts by mass of butyl acetate was continuously supplied to the reactor over 4 hours, and the external temperature was controlled so that the reaction temperature in the reactor could be kept constant at 80 ° C. After completion of liquid feeding at the same temperature, 0.65 parts by mass of AIVN was added and aged for 1 hour. The BA reaction rate was 97%, and the AA reaction rate was 98%. Thereto, 17 parts by mass of 4HBAGE and 6.5 parts by mass of TBAB were added and reacted at 80 ° C. for 6 hours. At this time, the reaction rate of 4HBAGE was 96%. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 550 parts by mass of a polymer. The properties of the polymer were Mw 76000, Mn 19600, Mw / Mn 3.90, E-type viscosity (25 ° C.) 500000 mPa · s. The number f of acryloyl groups per one polymer chain of the polymer was 2.7.

(Manufacturing method of polymer J) In a 1-liter pressurized stirring layer reactor equipped with an oil jacket, 75 parts by mass of 2-hydroxyethyl disulfide was charged, and the jacket temperature was raised so that the internal temperature would be 100 ° C. It was. Then, 0.9 parts by mass of AIVN dissolved in 64 parts by mass of BA was continuously supplied to the reactor over 30 minutes, and the external temperature was controlled so that the reaction temperature in the reactor was kept constant at 100 ° C. Thereafter, the reaction was further continued for 30 minutes at the same temperature. At this time, the reaction rate of BA was 98%. Subsequently, this solution was transferred to a separation coat, 100 parts by mass of toluene was added, and after shaking well, the solution was allowed to stand for a while to remove the lower layer (2-hydroxy sulfide) separated into two phases, and the toluene layer was evaporated. And dried under reduced pressure. 50 parts by mass of the resulting polymer was dissolved in 50 parts by mass of butyl acetate, the solution was put into a flask, 2 parts by mass of AOI and 1.1 parts by mass of TBAB were added, and the reaction was continued for 8 hours at 85 ° C. At this time, the reaction rate of AOI was 96%. After cooling, the reaction solution was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 50 parts by mass of a polymer. The properties of the polymer were Mw 34000, Mn 7700, Mw / Mn 4.4, E-type viscosity (25 ° C.) 88000 mPa · s. The number f of acryloyl groups per one polymer chain of the polymer was 1.7.

Compositions shown in Table 2 were prepared using the polymers A and C. The unit of the amount is part by mass. These compositions were filled into a mold and cured at 150 ° C. for 5 minutes to obtain a rubber-like cured product.
The abbreviations in Table 2 indicate the following.
-IBXA: Isoboronyl acrylate-Niper BW: Benzoyl peroxide, manufactured by NOF Corporation

  About the obtained hardened | cured material, the gel fraction was measured (Table 2). However, the gel fraction was calculated | required by the weight ratio of the hardened | cured material before extraction of the uncured part of hardened | cured material, and after extraction. Extraction of the uncured portion was performed by immersing the cured product in toluene.

  Since the sealing material composition of the present invention has excellent weather resistance, heat resistance, and the like, it can be widely applied in architectural applications, automobile-related applications, electrical / electronic applications, and the like.

Claims (5)

A sealing material composition containing a vinyl polymer having at least one (meth) acryloyl group per molecule at the molecular end, wherein the vinyl polymer starts polymerization of the compound represented by the general formula (1) A sealing material composition, wherein the vinyl monomer is produced by living radical polymerization as an agent.

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ² represents an alkyl group or nitrile group having 1 to ² carbon atoms, and R ³ represents — (CH ₂ ) m — (m R ⁴ and R ⁵ are each independently an alkyl group having 1 to 4 carbon atoms. ]   The sealing material composition according to claim 1, wherein the vinyl polymer is a (meth) acrylic polymer.   The number average molecular weight of the said vinyl polymer is 3000-50000, The sealing material composition of Claim 1 or 2 characterized by the above-mentioned.   The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the vinyl polymer is less than 2.0, according to any one of claims 1 to 3. The sealing material composition as described. The vinyl polymer can be converted to a carboxyl group at the terminal by living radical polymerization of a vinyl monomer containing a carboxyl group represented by the general formula (2) using the compound represented by the general formula (1) as a living radical polymerization initiator. It is a vinyl polymer produced by producing a vinyl polymer having a group and reacting the vinyl polymer with a glycidyl compound having a methacryloyl group represented by the general formula (3). The sealing material composition according to any one of claims 1 to 4.

Wherein, R ⁶ is a hydrogen atom or a methyl group, it may or may not be R ⁷ is a, if having R ⁷ is, -C (O) -O -, - OC (O) -, - NH— or —C ₆ H ₄ —, R ⁸ is R ⁹ —O— (R ⁹ is an alkyl group having 2 to 4 carbon atoms), R ¹⁰ —C (O) —O— (R ¹⁰ is carbon number) 1-8 alkyl group), R ¹¹ —O—C (O) —R ¹² — (R ¹¹ is an alkyl group having 1 to 8 carbon atoms, R ¹² is an alkyl group having 1 to 8 carbon atoms), —C ₆ H ₄ — or —CH ₂ ═CH ₂ —, and n is 0 to 4. ]

Wherein, R ¹³ is a hydrogen atom or a methyl group, may or may not be R ¹⁴ is a, if having a R ¹⁴ are, -C (O) -O -, - OC (O) -, - NH— or —C ₆ H ₄ —,
R ¹⁵ is R ¹⁶ —O— (R ¹⁶ is an alkyl group having 2 to 4 carbon atoms), R ¹⁷ —C (O) —O— (R ¹⁷ is an alkyl group having 1 to 8 carbon atoms), R ¹⁸ —O —C (O) —R ¹⁹ — (R ¹⁸ is an alkyl group having 1 to 8 carbon atoms, R ¹⁹ is an alkyl group having 1 to 8 carbon atoms), —C ₆ H ₄ — or —CH ₂ ═CH ₂ —. Yes, n is 0-4. ]