JP5593822B2 - Polysulfide sealant composition - Google Patents

Description

  The present invention relates to a polysulfide-based sealant composition.

  Conventionally, a silicone polymer having a reactive group, a polysulfide polymer having a reactive group, a modified polysulfide polymer having a reactive group, an acrylic urethane polymer having a reactive group, and a reactive group having a polymerization unit based on a fluoroolefin are included. At least one reaction-curable polymer (A) selected from a fluoropolymer, a saturated hydrocarbon polymer having a hydrolyzable silicon group, and an acrylic polymer having a hydrolyzable silicon group, and an acryloyl group and / or methacryloyl A curable composition characterized by containing a polyoxyalkylene compound (B) having a terminal group has been proposed (Patent Document 1).

JP 2003-2976 A

However, the present inventor has found that there is room for improvement in durability of the polysulfide-based sealing material composition containing a polyoxyalkylene compound having a (meth) acryloyl group at the terminal.
Then, an object of this invention is to provide the polysulfide type sealing material composition excellent in durability.

  As a result of earnest research to solve the above problems, the present inventor has a first liquid containing a polysulfide polymer having two or more thiol groups and a second liquid containing a urethane prepolymer, and further, an epoxy group , A reactive monomer having at least two functional groups A selected from the group consisting of (meth) acryloyloxy group, maleic anhydride group and maleimide group, epoxy group, (meth) acryloyloxy group, maleic anhydride It has been found that a composition having a reactive polymer having at least one functional group B selected from the group consisting of an acid group and a maleimide group can be a polysulfide-based sealing material composition having excellent durability. Completed the invention.

That is, this invention provides the following 1-7.
1. A first liquid comprising a polysulfide polymer having two or more thiol groups;
A second liquid containing a urethane prepolymer,
Furthermore, a reactive monomer having two or more functional groups A selected from the group consisting of an epoxy group, a (meth) acryloyloxy group, a maleic anhydride group and a maleimide group,
A polysulfide-based sealing material composition comprising a reactive polymer having at least one functional group B selected from the group consisting of an epoxy group, a (meth) acryloyloxy group, a maleic anhydride group and a maleimide group.
2. 2. The polysulfide-based sealing material composition according to 1 above, wherein the molecular weight of the reactive monomer is less than 500, and the weight average molecular weight of the reactive polymer is 500 or more.
3. The polysulfide-based sealing according to 1 or 2 above, wherein the amount of the reactive polymer is 1 to 25 parts by mass and the amount of the reactive monomer is 1 to 25 parts by mass with respect to 100 parts by mass of the first liquid. Material composition.
4). Any of the above 1-3, wherein the amount of the reactive polymer is 10 to 80% by mass and the amount of the reactive monomer is 20 to 90% by mass in the total amount of the reactive polymer and the reactive monomer. A polysulfide sealant composition according to claim 1.
5. The polysulfide-based sealing material composition according to any one of the above 1 to 4, wherein the functional group A and the functional group B are different.
6). The combination of the reactive polymer and the reactive monomer is
2 at least one functional group selected from the group consisting of a reactive polymer having two or more epoxy groups and / or a reactive polymer having two or more (meth) acryloyloxy groups and a maleic anhydride group and a maleimide group A combination with more than one reactive monomer,
At least one functional group selected from the group consisting of a reactive polymer having two or more epoxy groups and / or a reactive polymer having two or more (meth) acryloyloxy groups, and an epoxy group and a (meth) acryloyloxy group A combination with a reactive monomer having two or more, and
Selected from the group consisting of a reactive polymer having at least two functional groups selected from the group consisting of maleic anhydride groups and maleimide groups and epoxy groups, (meth) acryloyloxy groups, maleic anhydride groups and maleimide groups 5. The polysulfide-based sealing material composition according to any one of the above 1 to 4, which is at least one selected from the group consisting of a combination with a reactive monomer having two or more functional groups A.
7). The polysulfide-based sealing material composition according to any one of the above 1 to 6, substantially free of lead dioxide.

  The polysulfide-based sealing material composition of the present invention is excellent in durability.

The present invention will be described in detail below.
The polysulfide-based sealing material composition of the present invention comprises:
A first liquid comprising a polysulfide polymer having two or more thiol groups;
A second liquid containing a urethane prepolymer,
Furthermore, a reactive monomer having two or more functional groups A selected from the group consisting of an epoxy group, a (meth) acryloyloxy group, a maleic anhydride group and a maleimide group,
And a reactive polymer having two or more functional groups B selected from the group consisting of an epoxy group, a (meth) acryloyloxy group, a maleic anhydride group and a maleimide group.
Hereinafter, the polysulfide-based sealant composition of the present invention may be referred to as “the composition of the present invention”.

The polysulfide polymer will be described below.
In the composition of the present invention, the polysulfide polymer contained in the first liquid has two or more thiol groups (SH groups) in one molecule and contains a polysulfide bond in the main chain.

The polysulfide polymer is not particularly limited. For example, a conventionally well-known thing is mentioned. Specific examples of the polysulfide polymer include those represented by the following formulas (A) and (B).
(In the formula, each R independently represents C ₂ H ₄ OCH ₂ OC ₂ H ₄ or an alkylene group having 1 to 12 carbon atoms, x represents each independently an integer of 2 to 5, and m represents 1 independently. Represents an integer of ˜1500.)
x is preferably 2.

In the polysulfide polymer, the structural unit represented by-(R-S _x )-preferably forms all (100% by mass) of the main chain, and even when it contains other structural units, 5 It is preferable to form ~ 95 mass%.

  Commercially available products can be used as the polysulfide polymer, and specific examples thereof include THIOPLAST polymer manufactured by AKZO NOBEL, LP polymer manufactured by Toray Fine Chemical Co., Ltd. (manufactured by Toraythiol Co., Ltd.), and the like.

The number average molecular weight of the polysulfide polymer is usually preferably 300 to 200,000, and more preferably 500 to 50,000.
The polysulfide polymer is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
Polysulfide polymers can be used alone or in combination of two or more.

The urethane prepolymer will be described below.
In the composition of the present invention, the urethane prepolymer contained in the second liquid is not particularly limited. For example, a conventionally well-known thing is mentioned. Specifically, for example, a reaction product obtained by reacting a polyol and a polyisocyanate so that an isocyanate group becomes excessive with respect to a hydroxy group can be mentioned. The urethane prepolymer preferably contains 0.5 to 5% by mass of NCO groups at the molecular ends.

The polyisocyanate used when producing the urethane prepolymer is not particularly limited as long as it has two or more isocyanate groups in the molecule.
Specific examples of the polyisocyanate compound include TDI (for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI)), MDI ( For example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diene Aromatic polyisocyanates such as isocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; Aliphatic polyisocyanates such as socyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatomethyl) cyclohexane (H ₆ XDI), cycloaliphatic polyisocyanates such as dicyclohexylmethane diisocyanate (H ₁₂ MDI); carbodiimide-modified polyisocyanates; and isocyanurate-modified polyisocyanates.

A polyisocyanate compound can be used individually or in combination of 2 types or more, respectively.
Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), and hexamethylene diisocyanate (HDI), the resulting urethane prepolymer has a low viscosity and is easy to handle, It is preferable because of excellent compatibility and foam resistance and excellent curability.

The polyol used when producing the urethane prepolymer is not particularly limited as long as it has two or more hydroxy groups.
Polyols include, for example, polyoxyalkylene polyols; polyester polyols; polymer polyols; polycarbonate polyols; polybutadiene polyols; hydrogenated polybutadiene polyols; acrylic polyols; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol. And low molecular weight polyols such as hexanediol.
Of these, polyoxyalkylene polyols are preferred from the viewpoints of excellent compatibility and foam resistance, and excellent strength and elongation of the cured product.

  Examples of the polyoxyalkylene polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, Polyol obtained by adding at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and polyoxytetramethylene oxide to at least one selected from the group consisting of 1,4-butanediol and pentaerythritol Etc. Specifically, polyoxyethylene diol, polyoxyethylene triol, polyoxypropylene diol, and polyoxypropylene triol are preferably exemplified.

The polyols can be used alone or in combination of two or more.
The polyol is preferably a polyoxyalkylene polyol, and is preferably a polyoxypropylene diol or a polyoxypropylene triol, from the viewpoints of excellent compatibility and foam resistance, and excellent strength and elongation of the cured product.
The number average molecular weight of the polyol is preferably from 400 to 10,000, and preferably from 400 to 8,000, from the viewpoints of excellent compatibility and foam resistance and excellent strength and elongation of the cured product.

  In the present invention, the combination of the polyol compound and the polyisocyanate compound in producing the urethane prepolymer is selected from the group consisting of tolylene diisocyanate (TDI), xylylene diisocyanate (XDI) and diphenylmethane diisocyanate (MDI). A combination of at least one of the above and a polyoxyalkylene polyol (particularly polyoxypropylene diol and / or polyoxypropylene triol) is preferably exemplified.

  The amount of the polyisocyanate and the polyol when the urethane prepolymer is produced is such that the NCO group / OH group (equivalent ratio) is preferably 1.2 to 2.5, and more preferably 1.5 to 2.0. Is more preferable. When the equivalence ratio is within such a range, the viscosity of the obtained urethane prepolymer becomes appropriate, and the remaining amount of the unreacted polyisocyanate compound in the urethane prepolymer can be reduced.

The method for producing the urethane prepolymer is not particularly limited. For example, a conventionally well-known thing is mentioned.
A urethane prepolymer can be used individually or in combination of 2 types or more, respectively.

  The amount of the urethane prepolymer is the thiol group of the polysulfide polymer contained in the first liquid of the isocyanate group of the urethane prepolymer in the second liquid from the viewpoint of excellent properties of the cured product and excellent foam resistance. The equivalent ratio (isocyanate group / thiol group) to is preferably 0.7 to 1.3, more preferably 0.85 to 1.15.

The reactive monomer will be described below.
The reactive monomer used in the composition of the present invention is a compound having two or more functional groups A selected from the group consisting of epoxy groups, (meth) acryloyloxy groups, maleic anhydride groups and maleimide groups It is.
In the present invention, the (meth) acryloyloxy group means one or both of an acryloyloxy group and a methacryloyloxy group.
The structure other than the functional group A of the reactive monomer is not particularly limited as long as it is a divalent or higher organic group. The organic group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
The reactive monomer may be an oligomer. When the reactive monomer is an oligomer, the functional group A is preferably bonded at least to both ends of the oligomer from the viewpoint of superior durability.
When the reactive monomer is an oligomer, examples of its main chain include polyoxyalkylene and epoxy resin.
Examples of reactive monomers include reactive monomers having two or more epoxy groups, reactive monomers having two or more (meth) acryloyloxy groups, reactive monomers having two or more maleic anhydride groups, and maleimide groups. The reactive monomer which has 2 or more is mentioned.

The molecular weight of the reactive monomer is preferably less than 500, more preferably from 250 to less than 500, from the viewpoint that water resistance is superior.
In addition, with respect to the molecular weight of the reactive monomer, the reactive monomer having two or more (meth) acryloyloxy groups is preferably from 50 to less than 500 from the viewpoint of being excellent in water resistance, and other reactive monomers are Preferably it is less than 500.

<Reactive monomer having two or more epoxy groups>
The reactive monomer having two or more epoxy groups is not particularly limited as long as it is a monomer having two or more epoxy groups in one molecule.
One preferred embodiment is that the reactive monomer having two or more epoxy groups has a molecular weight of 50 or more and less than 500.

Specific examples of the reactive monomer having two or more epoxy groups include, for example, bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, and biphenyl type. Bifunctional glycidyl ether type epoxy resins such as epoxy compounds having a bisphenyl group, polyalkylene glycol type, alkylene glycol type epoxy compounds, epoxy compounds having a naphthalene ring, and epoxy compounds having a fluorene group;
Polyfunctional glycidyl ether type epoxy resins such as phenol novolac type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type;
Glycidyl ester epoxy resins of synthetic fatty acids such as dimer acid;
N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), tetraglycidyldiaminodiphenylsulfone (TGDDS), tetraglycidyl-m-xylylenediamine (TGMXDA) represented by the following formula (1), (2) represented by triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, N, N-diglycidylaniline, tetraglycidyl 1,3-bisaminomethylcyclohexane (TG1,3-BAC), tri Glycidylamine epoxy resin such as glycidyl isocyanurate (TGIC);

Tricyclo represented by the following formula (3) [5,2,1,0 ^2,6] epoxy compound having a decane ring (those having a molecular weight m is a mixture of 0 or 1 in the formula is less than 500), Specifically, for example, an epoxy compound that can be obtained by a known production method of reacting epichlorohydrin after polymerizing cresols or phenols such as dicyclopentadiene and metacresol;

Cycloaliphatic epoxy resin; epoxy resin represented by Toraythiol Co., Ltd. Frep 10 epoxy resin main chain having sulfur atom; urethane modified epoxy resin having urethane bond; polybutadiene, liquid polyacrylonitrile-butadiene rubber or acrylonitrile butadiene rubber Examples thereof include a rubber-modified epoxy resin containing (NBR).
These may be used alone or in combination of two or more.

  Of these epoxy resins, bisphenol A type epoxy resins are preferred because they are superior in durability, inexpensive and easily available.

  In the present invention, as the reactive monomer having two or more epoxy groups, commercially available products such as bisphenol A type epoxy resin (YD128, epoxy equivalent 190, manufactured by Tohto Kasei Co., Ltd.) can be used.

<Reactive monomer having two or more (meth) acryloyloxy groups>
The reactive monomer having two or more (meth) acryloyloxy groups is not particularly limited as long as it is a monomer having two or more (meth) acryloyloxy groups in one molecule.
The molecular weight of the reactive monomer having two or more (meth) acryloyloxy groups is preferably from 50 to less than 500, more preferably less than 500, from the viewpoint of superior durability.
The reactive monomer having two or more (meth) acryloyloxy groups may be an oligomer. Examples of the reactive monomer having two or more (meth) acryloyloxy groups are oligomers include polyoxyalkylene di (meth) acrylates such as polypropylene glycol di (meth) acrylate.
From the viewpoint that the molecular weight of the reactive oligomer having two or more (meth) acryloyloxy groups is more excellent in durability, it is preferably 50 to less than 500, and more preferably 200 to less than 500.

Specific examples of the reactive monomer having two or more (meth) acryloyloxy groups include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate , Pentaglycerol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di ( Such as (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate; polypropylene glycol di (meth) acrylate Examples include polyoxyalkylene di (meth) acrylate.
Of these, polypropylene glycol di (meth) acrylate is preferred because it is superior to durability, has low irritation to the skin, and is excellent in workability.

  In the present invention, as a reactive monomer having two or more (meth) acryloyloxy groups, a commercially available product such as polypropylene glycol di (meth) acrylate [trade name M220 (molecular weight: 300, manufactured by Toagosei Co., Ltd.)] is used. Can be used.

<Reactive monomer having two or more maleic anhydride groups>
The reactive monomer having two or more maleic anhydride groups is not particularly limited as long as it is a monomer having two or more maleic anhydride groups in one molecule.
The maleic anhydride group can be condensed with an aromatic hydrocarbon (eg, a benzene ring) to form a condensed polycycle. The same applies to a reactive polymer having two or more maleic anhydride groups.
One preferred embodiment is that the reactive monomer having two or more maleic anhydride groups has a molecular weight of 50 or more and less than 500.

Specific examples of the reactive monomer having two or more maleic anhydride groups include glycerin bisanhydro trimellitate monoacetate, ethylene glycol bisanhydro trimellitate, and the like.
Among these, glycerin bisahydrohydrotrimellitate monoacetate is preferable because it is superior in durability, is liquid, and has excellent workability.
One preferred embodiment of the reactive monomer having two or more maleic anhydride groups is a mixture of glycerin bisanhydro trimellitate monoacetate and alicyclic dicarboxylic acid anhydride.

  In the present invention, as a reactive monomer having two or more maleic anhydride groups, glycerin bisanhydro trimellitate monoacetate (Licacid TMTA-C, manufactured by Shin Nippon Rika Co., Ltd.), ethylene glycol bisanhydro trimellitate Commercially available products such as Ricacid TMEG-S (manufactured by Shin Nippon Rika Co., Ltd.) and ethylene glycol bisanhydro trimellitate (Ricacid TMEG-100, Shin Nippon Rika Co., Ltd.) can be used.

<Reactive monomer having two or more maleimide groups>
The reactive monomer having two or more maleimide groups is not particularly limited as long as it is a monomer having two or more maleimide groups in one molecule.
One preferred embodiment is that the reactive monomer having two or more maleimide groups has a molecular weight of 50 or more and less than 500.

Specific examples of the reactive monomer having two or more maleimide groups include 4,4′-diphenylmethane bismaleimide, bis (3-ethyl-5-methyl-maleimidophenyl) methane, and 2,2′-bis. And [4- (4-maleimidophenoxy) phenyl] propane.
Of these, bis (3-ethyl-5-methyl-maleimidophenyl) methane is preferred from the viewpoint of superior durability and excellent solubility.

  In the present invention, as a reactive monomer having two or more maleimide groups, bis (3-ethyl-5-methyl-maleimidophenyl) methane (BMI-70, manufactured by Kay Kasei Co., Ltd.), 2,2′- Commercially available products such as bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80, manufactured by Kay Chemical Co., Ltd.) can be used.

The reactive polymer will be described below.
The reactive polymer used in the composition of the present invention is a reaction having two or more functional groups B selected from the group consisting of epoxy groups, (meth) acryloyloxy groups, maleic anhydride groups and maleimide groups. Polymer.
The structure other than the functional group B of the reactive polymer is not particularly limited as long as it is a divalent or higher organic group. The organic group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
The functional group B is preferably bonded at least to both ends of the reactive polymer from the viewpoint of superior durability.
The reactive polymer may be an oligomer. When the reactive polymer is an oligomer, the functional group B is preferably at least bonded to both ends of the oligomer from the viewpoint of superior durability.
When the reactive polymer is an oligomer, examples of the main chain of the reactive polymer include diene polymers such as polybutadiene, urethane prepolymers, urethane resins, (meth) acrylic resins, and polyphenylmethane.
Examples of the reactive polymer include a reactive polymer having two or more epoxy groups, a reactive polymer having two or more (meth) acryloyloxy groups, a reactive polymer having two or more maleic anhydride groups, and a maleimide group. The reactive polymer which has 2 or more is mentioned.

The weight average molecular weight of the reactive polymer is preferably 500 or more, more preferably 500 to 10,000, from the viewpoint of superior water resistance.
Further, the molecular weight of the reactive polymer is preferably 500 to 10,000 for the reactive polymer having two or more (meth) acryloyloxy groups from the viewpoint of being excellent in water resistance, and the other reactive polymer is 500. The above is preferable.

<Reactive polymer having two or more epoxy groups>
The reactive polymer having two or more epoxy groups is not particularly limited as long as it has two or more epoxy groups (oxirane ring) in one molecule, and may be either a homopolymer or a copolymer. The weight average molecular weight of the reactive polymer having two or more epoxy groups is preferably 500 or more.

Specific examples of the reactive polymer having two or more epoxy groups include epoxidized natural rubber, epoxidized polybutadiene, styrenic elastomer having epoxide, and rubber-modified epoxy resin such as acrylic rubber having epoxide; ethylene Examples thereof include epoxy-modified acrylic resins such as glycidyl methacrylate-methyl acrylate copolymer and ethylene-glycidyl methacrylate-vinyl acetate copolymer.
Of these, epoxidized polybutadiene is preferred because it is superior in durability, has a low viscosity, and has good workability.

(Epoxidized natural rubber)
As said epoxidized natural rubber, what was obtained by epoxidizing natural rubber may be used, and a commercial item may be used.
The method for epoxidizing natural rubber is not particularly limited, and examples thereof include a chlorohydrin method, a direct oxidation method, a hydrogen peroxide method, an alkyl hydroperoxide method, and a peracid method. Specifically, there is a method of reacting natural rubber with an organic peracid such as peracetic acid or performic acid.
Further, as commercially available products, specifically, for example, ENR-25 (epoxidation rate: 25%), ENR-50 (epoxidation rate: 50%), ENR-60 (manufactured by Malaysian Rubber Bureau (MRB)) Epoxidation rate: 60%) and the like.

  Moreover, it is preferable that the epoxidation rate of the said epoxidized natural rubber is 5-80 mol%, and it is more preferable that it is 5-60 mol%.

(Epoxidized polybutadiene)
As said epoxidized polybutadiene, what is obtained by epoxidizing polybutadiene may be used, and a commercial item may be used.
The method of epoxidizing polybutadiene is not particularly limited, and examples thereof include a method of epoxidizing 1,2-polybutadiene so that oxirane oxygen is 5% or more by a hydrogen peroxide method or the like.
Moreover, as a commercial item, specifically, for example, Epolide PB3600 manufactured by Daicel Chemical Industries, Ltd. is exemplified.

(Acrylic rubber with epoxide)
Specific examples of the acrylic rubber having the epoxide include a monomer component that forms a main skeleton such as ethyl acrylate, butyl acrylate, and methoxyethyl acrylate, and a monomer component that forms a crosslinking point such as glycidyl acrylate and glycidyl methacrylate. May be obtained by copolymerizing with or a commercially available product.
Specific examples of commercially available products include Nipol AR30 series, 40 series, and 50 series manufactured by Nippon Zeon Co., Ltd. Among them, AR32, AR53L, and AR54 are preferable because of low Tg and excellent cold resistance. It is mentioned in.

(Styrenic elastomer with epoxide)
The styrene-based elastomer having the epoxide is a styrene-based thermoplastic elastomer whose hard segment is polystyrene and is an elastomer obtained by epoxidizing an unsaturated double bond portion contained in the conjugated diene component of the soft segment.
In the present invention, commercially available products such as Epofriend (for example, CT301, AT501) manufactured by Daicel Chemical Industries, Ltd. can be used.

(Ethylene-glycidyl methacrylate-methyl acrylate copolymer)
As the ethylene-glycidyl methacrylate-methyl acrylate copolymer, for example, commercially available products such as Bond First 7L and 7M manufactured by Sumitomo Chemical Co., Ltd. can be used.

(Ethylene-glycidyl methacrylate-vinyl acetate copolymer)
As the ethylene-glycidyl methacrylate-vinyl acetate copolymer, for example, commercially available products such as Bond Fast 2B and 7B manufactured by Sumitomo Chemical Co., Ltd. can be used.

  Among these, the reactive polymer having two or more epoxy groups is preferably a bifunctional epoxy from the viewpoint of being excellent in durability, liquid and excellent in dispersibility.

<Reactive polymer having two or more (meth) acryloyloxy groups>
The reactive polymer having two or more (meth) acryloyloxy groups is not particularly limited as long as it has two or more (meth) acryloyloxy groups in one molecule and has a weight average molecular weight of 500 or more. Either a homopolymer or a copolymer may be used.

Specific examples of the reactive polymer having two or more (meth) acryloyloxy groups include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, and γ. -Among homopolymers and copolymers such as methacryloxypropyltrimethoxysilane, those having (meth) acryloyloxy groups at both ends of the polymer; urethane (meth) acrylate and the like.
Of these, urethane (meth) acrylate is preferable from the viewpoint of superior durability.

(Urethane (meth) acrylate)
The urethane (meth) acrylate is not particularly limited as long as it is a polymer having a urethane bond and having two or more (meth) acryloyloxy groups in one molecule.
Examples of the urethane (meth) acrylate include those in which a main chain has a urethane bond and two or more (meth) acryloyloxy groups are bonded to the terminal or side chain of the main chain.
Specifically, a reaction product of a polyol compound, a polyisocyanate compound having two or more hydroxyl groups in one molecule, and a (meth) acrylate having a hydroxyl group and a (meth) acryloyloxy group in one molecule; Examples include isocyanate compounds and reaction products of (meth) acrylates having a hydroxyl group and a (meth) acryloyloxy group in one molecule.

Here, the reaction product of the polyol compound, the polyisocyanate compound, and the (meth) acrylate is obtained by reacting the polyol compound and the polyisocyanate compound to form a so-called urethane prepolymer having an isocyanate group. It is a product obtained by reacting.
Specifically, first, a polyol compound and a polyisocyanate compound are reacted so that an isocyanate group becomes an excess amount in the same manner as in the synthesis of a normal urethane prepolymer to produce a urethane prepolymer. In this reaction, the isocyanate group / hydroxyl group (equivalent ratio) is preferably 1.2 to 2.5, and more preferably 1.5 to 2.2.
Subsequently, urethane (meth) acrylate is produced | generated by making the isocyanate group of the obtained urethane prepolymer react with the hydroxyl group of (meth) acrylate.

  On the other hand, a reaction product of a polyisocyanate compound and (meth) acrylate is a product obtained by reacting an isocyanate group of a polyisocyanate compound with a hydroxyl group of acrylate.

If the said polyol compound used for the production | generation of the said urethane (meth) acrylate is a compound which has 2 or more of hydroxyl groups, the molecular weight, frame | skeleton, etc. will not be specifically limited, As a specific example, low molecular weight polyhydric alcohol, Examples thereof include polycarbonate polyol, polyether polyol, polyester polyol, other polyols, and mixed polyols thereof.
Specific examples of the polyol compound include conventionally known polyol compounds used for producing a urethane prepolymer.

Further, the polyisocyanate compound used for producing the urethane (meth) acrylate is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule. Specific examples thereof include TDI (for example, 2, 4). -Tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI)), MDI (for example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2, 4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphth Aromatic polyisocyanates such as diisocyanate (NDI), triphenylmethane triisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); Alicyclic polyisocyanates such as transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatemethyl) cyclohexane (H ₆ XDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI); these carbodiimide-modified polyisocyanates These isocyanurate-modified polyisocyanates; and the like.

  The (meth) acrylate used for the production of the urethane (meth) acrylate is an acrylate having a hydroxyl group and a (meth) acryloyloxy group in one molecule. Specific examples thereof include trimethylolpropane di (meth) ) Acrylate, pentaglycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and the like.

  In the present invention, commercial products such as urethane (meth) acrylate (CN968, aliphatic hexafunctional urethane oligomer, manufactured by Sartomer) can be used as the reactive polymer having two or more (meth) acryloyloxy groups.

<Reactive polymer having two or more maleic anhydride groups>
The reactive polymer having two or more maleic anhydride groups is not particularly limited as long as it has two or more maleic anhydride groups in one molecule and a weight average molecular weight of 500 or more. Homopolymers and copolymers Any of these may be used.

Specific examples of the reactive polymer having two or more maleic anhydride groups include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), ethylene- Elastomeric polymers such as diene rubbers such as propylene-diene rubber (EPDM) and butyl rubber (IIR), and olefin rubbers such as ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), and ethylene-butene rubber (EBM) For example, a maleic anhydride-modified rubber obtained by modifying a styrene with maleic anhydride; a copolymer of styrene and maleic anhydride; and the like.
Of these, a butadiene rubber modified with maleic anhydride is preferred because it is superior in durability, has a low viscosity, and has good workability. Also, a copolymer of styrene and maleic anhydride because it is superior in durability, has high crystallinity, has good drying properties, and can further suppress surface tack in the uncured state after the sealant is applied. Is preferred.

  The method of modifying the elastomeric polymer with maleic anhydride is not particularly limited, and examples thereof include a method of reacting an ethylenically unsaturated bond portion of maleic anhydride with the elastomeric polymer.

  In the present invention, as a reactive polymer having two or more maleic anhydride groups, butadiene rubber modified with maleic anhydride (POLYVESTTOC 800S, manufactured by Degussa), isoprene rubber having two or more maleic anhydride groups (L Commercially available products such as -IR-403 (manufactured by Kuraray Co., Ltd.) and a copolymer of styrene and maleic anhydride (SMA-EF80, manufactured by Sartomer Co., Ltd.) can be used.

  Reactive polymers having two or more maleic anhydride groups are excellent in durability, liquid and dispersible, from the viewpoint of butadiene rubber modified with maleic anhydride, isoprene rubber having two or more maleic anhydride groups. preferable.

<Reactive polymer having two or more maleimide groups>
The reactive polymer having two or more maleimide groups is not particularly limited as long as it has two or more maleimide groups in one molecule and has a weight average molecular weight of 500 or more, and may be either a homopolymer or a copolymer. May be.

  Specific examples of the reactive polymer having two or more maleimide groups include polyphenylmethane maleimide and the like.

In the present invention, commercial products such as polyphenylmethane maleimide (BMI-2300, manufactured by Daiwa Kasei Co., Ltd.) can be used as the reactive polymer having two or more maleimide groups.
The reactive polymer having two or more maleimide groups is preferably polyphenylmethane maleimide from the viewpoint of excellent durability and excellent solubility of a plasticizer or the like.

In the present invention, the amount of the reactive polymer is preferably 1 to 25 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polysulfide polymer, from the viewpoint of superior durability and excellent physical properties. Is more preferable.
The amount of the reactive polymer is preferably 1 to 25 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the first liquid, from the viewpoint of superior durability and excellent physical properties. preferable.

In the present invention, the amount of the reactive monomer is preferably 1 to 25 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polysulfide polymer, from the viewpoint of superior durability and excellent physical properties. Is more preferable.
The amount of the reactive monomer is preferably 1 to 25 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the first liquid from the viewpoint of superior durability and excellent physical properties. preferable.

  The amount of the reactive polymer is preferably 10 to 80% by mass in the total amount of the reactive polymer and the reactive monomer, and is preferably 25 to 75% by mass from the viewpoint of superior durability and excellent physical properties. Is more preferable.

  The amount of the reactive monomer is preferably 20 to 90% by mass in the total amount of the reactive polymer and the reactive monomer, and is preferably 25 to 75% by mass from the viewpoint of superior durability and excellent physical properties. Is more preferable.

In the present invention, the functional group A possessed by the reactive monomer and the functional group B possessed by the reactive polymer may be the same or different. From the viewpoint of superior durability and excellent physical properties, it is preferable that the functional group A of the reactive monomer and the functional group B of the reactive polymer are different.
As a combination of the reactive polymer and the reactive monomer in the preferred embodiment,
(1) A reactive polymer having two or more epoxy groups and / or a reactive polymer having two or more (meth) acryloyloxy groups, and at least one functional selected from the group consisting of a maleic anhydride group and a maleimide group In combination with a reactive monomer having two or more groups;
(2) At least one selected from the group consisting of a reactive polymer having two or more epoxy groups and / or a reactive polymer having two or more (meth) acryloyloxy groups, and an epoxy group and a (meth) acryloyloxy group In combination with a reactive monomer having two or more functional groups of
(3) A reactive polymer having at least two functional groups selected from the group consisting of a maleic anhydride group and a maleimide group, an epoxy group, a (meth) acryloyloxy group, a maleic anhydride group, and a maleimide group The combination with the reactive monomer which has 2 or more of the at least 1 sort (s) of functional group A chosen from a group is mentioned.

Specifically, for example,
A combination of a reactive polymer having two or more epoxy groups and a reactive monomer having two or more (meth) acryloyloxy groups;
A combination of a reactive polymer having two or more (meth) acryloyloxy groups and a reactive monomer having two or more maleic anhydride groups,
A combination of a reactive polymer having two or more maleic anhydride groups and a reactive monomer having two or more maleimide groups;
A combination of a reactive polymer having two or more maleic anhydride groups and a reactive monomer having two or more (meth) acryloyloxy groups;
Etc.
The combination of the reactive monomer and the reactive polymer is, among other things, superior in durability, excellent in physical properties and weather resistance, and includes a reactive polymer having two or more maleic anhydride groups and a (meth) acryloyloxy group. A combination with two or more reactive monomers is preferred.

  In addition, when a reactive polymer having two or more epoxy groups and a reactive monomer having two or more maleic anhydride groups are used in combination, a reactive polymer having two or more maleic anhydride groups and two epoxy groups are used. When using together with the reactive monomer which has the above, since a reactive polymer and a reactive monomer will react, it can use together by mixing just before construction.

The composition of the present invention only needs to have a reactive monomer, and one or both of the first liquid and the second liquid can contain the reactive monomer, or other than the first liquid and the second liquid. The third liquid can have a reactive monomer. The same applies to reactive polymers.
Specifically, for example, when at least the first liquid includes a reactive monomer and a reactive polymer, when at least the second liquid includes a reactive monomer and a reactive polymer, at least the first liquid and the second liquid are In the case where the reactive monomer and the reactive polymer are included, there is a case where at least the third liquid includes the reactive monomer and the reactive polymer.
When at least the first liquid and the second liquid contain the reactive monomer and the reactive polymer, the first liquid and the second liquid may contain the reactive monomer and the reactive polymer, respectively, and the first liquid contains the reactive monomer. The included second liquid may include a reactive polymer, the first liquid may include a reactive polymer, and the second liquid may include a reactive monomer.

  When the composition of the present invention has a third liquid, at least the third liquid may contain a reactive monomer and a reactive polymer. In this case, the first liquid and the second liquid may be free of reactive monomers and reactive polymers.

The composition of this invention is mentioned as one of the aspects with preferable lead dioxide substantially not containing lead dioxide from a viewpoint of being excellent in durability and excellent in environmental load.
In the present invention, the phrase “substantially free of lead dioxide” means that the amount of lead dioxide in the entire composition of the present invention is 0 to 1% by mass or less.

  The composition of this invention can contain an additive in the range which does not impair the objective of this invention as needed. Examples of additives include plasticizers, fillers (for example, calcium carbonate, surface-treated calcium carbonate, resin hollow bodies), curing catalysts, thixotropic agents, silane coupling agents, pigments, dyes, anti-aging agents. , Antioxidants, antistatic agents, flame retardants, drying oils, adhesion-imparting agents, dispersants, dehydrating agents, ultraviolet absorbers, and solvents.

The composition of the present invention is not particularly limited for its production. For example, when one or both of the first liquid and the second liquid contain a reactive monomer and a reactive polymer, one or both of the first liquid and the second liquid are reactive with the reactive monomer. A polymer is added to prepare a first liquid (main agent) containing a polysulfide polymer and a second liquid (curing agent) containing a urethane prepolymer, which are separately mixed under a nitrogen gas atmosphere. Can do.
When the third liquid contains a reactive monomer and a reactive polymer, the first liquid (main agent) containing a polysulfide polymer, the second liquid (curing agent) containing a urethane prepolymer, the reactive monomer and the reactivity It can be prepared by a method in which the third liquid containing the polymer is separately sufficiently mixed under a nitrogen gas atmosphere.
The composition of the present invention can be used by thoroughly mixing and using the first liquid (main agent) and the second liquid (curing agent).
The composition of the present invention can be used by thoroughly mixing and using the first liquid (main agent), the second liquid (curing agent), and the third liquid.

Examples of the use of the composition of the present invention include a sealing material and an adhesive.
Examples of the adherend to which the composition of the present invention can be applied include mortar, concrete, metal, painted plate, plastic, and rubber.
The method for applying the composition of the present invention to an adherend is not particularly limited. For example, a conventionally well-known thing is mentioned.
The composition of the present invention can be cured by heating, for example, moisture such as moisture.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Evaluation>
The durability of the composition obtained as described below was evaluated by the following method. The results are shown in Table 1.
4.4.3 of JIS A5758: 2004 Appropriateness of classification by durability, classification by durability: 9030 and classification by main component: combination of polysulfide type, JIS A1439: 2004 5.17 (durability test) Tested by The test body uses anodized aluminum as an adherend, and uses a composition manufactured as follows as a sample. FIG. 14 Durability test body (b) of 5.17.2 of JIS A1439: 2004 It was produced according to type 2. The curing conditions were 23 (± 2) ° C. and 50 (± 5)% RH for 7 days for the pre-curing, and 7 days for the post-curing for 50 (± 2) ° C. The procedure of the durability test conformed to Table 4 (a) Durability test procedure (1) of 5.17.3 of JIS A1439: 2004.

Dissolution, swelling, cracks, wrinkles, cracks, peeling from the adherend, deformation of the outer shape, and the like of the test body were visually confirmed, and the results were evaluated according to the following evaluation criteria.
○: When there is no appearance abnormality such as cracks or cracks on the appearance or peeling.
Δ: There are cracks, wrinkles, etc. on the surface of the specimen, but there is no peeling, cracking or deformation of the outer shape.
X: When there are abnormalities such as cracks, deformation on the outer shape and peeling.

<Production of composition>
Using the components shown in Table 1 in the amounts (parts by mass) shown in the same table, these were uniformly mixed to produce a composition. In addition, the 2nd liquid (curing agent of brand name SC-M500, the product made from Yokohama Rubber Co., Ltd.) of the polysulfide type sealing material composition containing isocyanate is used as a 2nd liquid, and this was mixed with the component shown in Table 1. .

Each component shown in Table 1 is as follows.
-1st liquid: The 1st liquid of the polysulfide-type sealing material composition containing a polysulfide polymer (the main ingredient of brand name SC-M500, the Yokohama Rubber company make)
-Reactive polymer 1: Epoxidized polybutadiene (Epolide PB3600, weight average molecular weight: 2800, epoxy equivalent: 188-213, manufactured by Daicel Chemical Industries, Ltd., having 13-15 epoxy groups per molecule)
-Reactive polymer 2: Urethane (meth) acrylate (CN968, aliphatic hexafunctional urethane oligomer, weight average molecular weight: 1400, manufactured by Sartomer Co., which has an average of 6 (meth) acrylate groups per molecule)
-Reactive polymer 3: Maleic anhydride-modified polybutadiene (POLYVESTTOC800S, weight average molecular weight: 2500, manufactured by Degussa, Inc. has an average of 1.4 maleic anhydride groups per molecule)
Reactive polymer 4: Polyphenylmethane maleimide (BMI-2300, weight average molecular weight: 670, manufactured by Daiwa Kasei Kogyo Co., Ltd., having an average of 3 maleimide groups per molecule)
Reactive monomer 1: Bisphenol A type epoxy resin (YD128, molecular weight: 340, epoxy equivalent: 190, manufactured by Tohto Kasei Co., Ltd., having two epoxy groups per molecule)
Reactive monomer 2: Polypropylene glycol di (meth) acrylate (trade name M220 (Molecular weight: 300, manufactured by Toa Gosei Co., Ltd., having two (meth) acrylate groups per molecule at both ends)
-Reactive monomer 3: Mixture of glycerin bisanhydro trimellitate monoacetate and alicyclic dicarboxylic acid anhydride (MTA-15, molecular weight: 482, manufactured by Shin Nippon Rika Co., Ltd.)
Reactive monomer 4: bis (3-ethyl-5-methyl-maleimidophenyl) methane (BMI-70, molecular weight: 442, manufactured by Kay Kasei Co., Ltd.)

As is clear from the results shown in Table 1, Comparative Examples 1 to 4 not containing a reactive monomer and Comparative Examples 5 to 8 not containing a reactive polymer were inferior in durability.
On the other hand, Examples 1-13 are excellent in durability.

Claims (5)

A first liquid comprising a polysulfide polymer having two or more thiol groups;
A second liquid containing a urethane prepolymer,
Furthermore, a reactive monomer having two or more functional groups A selected from the group consisting of an epoxy group, a (meth) acryloyloxy group, a maleic anhydride group and a maleimide group,
Epoxy group, possess a (meth) acryloyloxy group, reactive polymers having at least one two or more functional groups B are selected from the group consisting of maleic anhydride groups and maleimide groups,
The molecular weight of the reactive monomer is less than 500, the weight average molecular weight of the reactive polymer is 500 to 10,000,
The polysulfide-based sealing material composition , wherein the amount of the reactive polymer is 1 to 25 parts by mass and the amount of the reactive monomer is 1 to 25 parts by mass with respect to 100 parts by mass of the first liquid . During the total amount of the reactive monomer and the reactive polymer, the amount of the reactive polymer is 10 to 80 mass%, according to claim 1 the amount of the reactive monomer is 20 to 90 wt% Polysulfide sealant composition. The polysulfide-based sealing material composition according to claim 1 or 2 , wherein the functional group A and the functional group B are different. The combination of the reactive polymer and the reactive monomer is
2 at least one functional group selected from the group consisting of a reactive polymer having two or more epoxy groups and / or a reactive polymer having two or more (meth) acryloyloxy groups and a maleic anhydride group and a maleimide group A combination with more than one reactive monomer,
At least one functional group selected from the group consisting of a reactive polymer having two or more epoxy groups and / or a reactive polymer having two or more (meth) acryloyloxy groups, and an epoxy group and a (meth) acryloyloxy group A combination with a reactive monomer having two or more, and
Selected from the group consisting of a reactive polymer having at least two functional groups selected from the group consisting of maleic anhydride groups and maleimide groups and epoxy groups, (meth) acryloyloxy groups, maleic anhydride groups and maleimide groups The polysulfide-based sealing material composition according to claim 1 or 2 , which is at least one selected from the group consisting of a combination with a reactive monomer having two or more functional groups A. The polysulfide-based sealing material composition according to any one of claims 1 to 4 , which does not substantially contain lead dioxide.