JP2007070519A - Sealing material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealing material composition which well maintains physical properties after cured and has an excellent hydrolysis resistance. <P>SOLUTION: The sealing material composition is obtained by the reaction of (A) a polysulfide polyether polymer containing not less than two thiol groups in one molecule, (B) a hydroxyl group-containing acrylic polymer, hexamethylene diisocyanate and a polyol compound and contains (C) a urethane prepolymer having not less than two isocyanate groups in one molecule and (D) a liquid hindered phenol. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a sealant composition.

As a polysulfide-based sealing material composition containing a thiol group-containing polysulfide polymer and a compound having two or more isocyanate groups (NCO groups) in one molecule (hereinafter referred to as “polyisocyanate compound”), one molecule A curable composition containing a polymer having two or more thiol groups therein and a polyisocyanate compound is known.
This composition has better dynamic durability than conventional polysulfide-based sealants by oxidizer curing, and is non-staining that does not contaminate the surface of the cured product outdoors like conventional products. Since it is excellent, it can be used in many applications as a sealing material, an adhesive, and a coating material for construction, civil engineering, automobiles, and aircrafts.

However, although such a composition has good weather resistance with a resin alone, the viewpoint of improving the economic properties and physical properties after curing when the composition is applied (for example, modulus, elongation at break, strength at break). When using a plasticizer, a filler, and an additive, the weather resistance may be lowered.
Therefore, it is desired to provide a curable composition (sealing material composition) that has good weather resistance even when it contains a plasticizer, a filler, and an additive, and is suitable for use as a sealing material. Patent Document 1 states that “(a) a polymer containing two or more thiol groups in one molecule; (b) a compound containing two or more isocyanate groups in one molecule; and (c) carbonization. A curable composition comprising a hydrogen-based polymer and / or (d) a photocurable compound has been proposed.

JP 2003-306525 A

  However, it has been clarified that the curable composition described in Patent Document 1 may not have sufficient hydrolysis resistance under high temperature and high humidity conditions.

  Then, this invention makes it a subject to provide the sealing material composition which is excellent also in hydrolysis resistance, maintaining the physical property after hardening favorable.

  As a result of intensive studies to solve the above problems, the inventor of the present invention uses a urethane prepolymer synthesized using hexamethylenediamine (HDI) as a polyisocyanate component as a curing agent component, a polysulfide polyether polymer, a hydroxyl group (OH). A curable composition using an acrylic polymer having a group) and a specific hindered phenol as a main component, and a sealing material composition having excellent hydrolysis resistance while maintaining good physical properties after curing. And the present invention was completed.

That is, the present invention provides the following sealing material compositions (1) to (3).
(1) It is obtained by reacting a polysulfide polyether polymer (A) having two or more thiol groups in one molecule, a hydroxyl group-containing acrylic polymer (B), HDI and a polyol compound, and 2 in one molecule. A sealing material composition containing a urethane prepolymer (C) having at least one isocyanate group and a liquid hindered phenol (D).
(2) The content of the hydroxyl group-containing acrylic polymer (B) is 5 to 40 parts by mass with respect to a total of 100 parts by mass of the polysulfide polyether polymer (A) and the hydroxyl group-containing acrylic polymer (B). The sealing material composition according to (1) above.
(3) The sealing material according to (1) or (2), wherein the liquid hindered phenol (D) is 4,6-bis (octylthiomethyl) -o-cresol represented by the following structural formula: Composition.

  As will be described below, the present invention is useful because it can provide a sealing material composition that is excellent in hydrolysis resistance while maintaining good physical properties after curing.

The present invention is described in detail below.
The sealing material composition of the present invention is obtained by reacting a polysulfide polyether polymer (A) having two or more thiol groups in one molecule, a hydroxyl group-containing acrylic polymer (B), HDI and a polyol compound. It is a curable composition containing a urethane prepolymer (C) having two or more isocyanate groups in one molecule and a liquid hindered phenol (D).
Next, the polysulfide polyether polymer (A), the hydroxyl group-containing acrylic polymer (B), the urethane prepolymer (C) and the liquid hindered phenol (D) used in the sealing material composition of the present invention will be described in detail.

<Polysulfide polyether polymer (A)>
The polysulfide polyether polymer (A) used in the sealing material composition of the present invention is a kind of polysulfide polymer, has two or more thiol groups (SH groups) in one molecule, and has an ether bond in the main chain. Is included.

As such polysulfide polyether polymer (A), specifically,
In the main chain, (1) - and represented by polyether moiety (wherein, R ₁ represents an alkylene group having 2 to 4 carbon atoms, n is an integer of 6 to 200.) - (R ₁ O) _n , (2)-(C ₂ H ₄ OCH ₂ OC ₂ H ₄ —S _x ) — and — (CH ₂ CH (OH) CH ₂ —S _x ) — (where x is 1) An integer of ~ 5).
And (3) —C ₂ H ₄ OCH ₂ OC ₂ H ₄ —SH and / or a thiol group represented by —CH ₂ CH (OH) CH ₂ —SH; Is done.

In the polysulfide polyether polymer represented by this specific example, the polyether moiety (1) and the structural unit represented by (2) may be bonded in an arbitrary arrangement. The ratio of (1)-(R ¹ O) _n -component is 2 to 95% by mass, and (2)-(C ₂ H ₄ OCH ₂ OC ₂ H ₄ -S _X ) -component is 3 70 wt%, _{and, - (CH 2 CH (OH} ) CH 2 -S x) - it is preferred that the component is 1 to 50 mass%.

  Commercially available products can be used as the polysulfide polyether polymer (A), and specific examples thereof include LP282 manufactured by Toray Fine Chemical Co., Ltd. used in the examples.

  In the present invention, the number average molecular weight of the polysulfide polyether polymer (A) is usually preferably 600 to 200,000, and more preferably 800 to 50,000.

  In the present invention, the polysulfide polyether polymer (A) is, for example, a halogen-terminated prepolymer obtained by adding an epihalohydrin to a polyoxyalkylene glycol as described in JP-A-4-363325. And a polysulfide polymer in a mass ratio of 95/5 to 5/95 can be produced together with an alkali hydrosulfide and / or an alkali polysulfide.

<Hydroxyl-containing acrylic polymer (B)>
The hydroxyl group-containing acrylic polymer (B) used in the sealing material composition of the present invention is not particularly limited as long as it is an acrylic polymer having a hydroxyl group, and examples thereof include a (meth) acrylate homopolymer having a hydroxyl group. Preferably mentioned.

  Specific examples of the (meth) acrylate having a hydroxyl group include, for example, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-3-hydroxypropyl, and (meth) acrylic acid-4-hydroxybutyl. Compounds obtained by ring-opening addition of ε-caprolactam, ethylene oxide, etc .; (meth) acrylic acid and various compounds such as ethylene glycol, ethylene oxide, propylene glycol, propylene oxide, butylene glycol, cyclohexanedimethanol, glycerin, trimethylolpropane, etc. A monomer that is a reaction product with a monohydric alcohol; and the like. These may be used alone or in combination of two or more.

  Commercially available products can be used as the hydroxyl group-containing acrylic polymer (B), and specific examples thereof include UH2000 manufactured by Toagosei Co., Ltd. used in the examples.

  By using such a hydroxyl group-containing acrylic polymer (B), it is possible to suppress physical properties after curing of the sealing material composition of the present invention obtained, in particular, changes in physical properties of the cured product after heat resistance.

  In this invention, content of the said hydroxyl-containing acrylic polymer (B) is 5-40 mass parts with respect to a total of 100 mass parts of the said polysulfide polyether polymer (A) and a hydroxyl-containing acrylic polymer (B). It is preferable that it is 20-30 parts by mass. When the content range is within this range, the cured product properties after standard curing of the obtained sealing material composition of the present invention will be better, and the physical property variation of the cured product after heat resistance may be sufficiently reduced. it can.

<Urethane prepolymer (C)>
The urethane prepolymer (C) used in the sealing material composition of the present invention is a urethane prepolymer obtained by a reaction of HDI and a polyol compound and having two or more isocyanate groups in one molecule. Similar to the liquid polyurethane resin composition, it is a reaction product obtained by reacting a polyol compound with an excess of HDI (that is, an excess of NCO groups with respect to OH groups). An NCO group is contained at the molecular end.

  By using HDI as the polyisocyanate compound for producing the urethane prepolymer (C), the hydrolysis resistance of the obtained sealing material composition of the present invention can be improved.

In the present invention, other polyisocyanate compounds can be used in combination with HDI. In addition, when using another polyisocyanate compound together, it is preferable that the content is 9-0.25 molar ratio (HDI / other polyisocyanate compound) of HDI and other polyisocyanate.
Other polyisocyanate compounds are not particularly limited as long as they are compounds having two or more NCO groups in the molecule. Specific examples thereof include 2,4-tolylene diisocyanate (2,4-TDI), 2,6. -Tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate , Aromatic polyisocyanates such as xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI); trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate Ne Aliphatic polyisocyanates such as norbornane diisocyanate methyl (NBDI); trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), _{H 12} MDI (hydrogenated MDI), H ₆ Cycloaliphatic polyisocyanates such as TDI (hydrogenated TDI); Polyisocyanate compounds such as polymethylene polyphenylene polyisocyanate; Carbodiimide-modified polyisocyanates of these isocyanate compounds; Isocyanurate-modified polyisocyanates of these isocyanate compounds; Urethane prepolymers obtained by reacting a compound with a polyol compound described later; and the like. These may be used alone or in combination of two or more.

  On the other hand, the polyol compound that generates the urethane prepolymer (C) is not particularly limited in terms of its molecular weight and skeleton as long as it is a compound having two or more OH groups. Specific examples thereof include low molecular weight polyhydric alcohols. , Polyether polyols, polyester polyols, other polyols, and mixed polyols thereof.

  Here, specific examples of the low-molecular polyhydric alcohols include ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, and (1,3- or 1,4-) butanediol. , Pentanediol, neopentyl glycol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, low molecular polyols such as pentaerythritol; sorbitol, etc. Saccharides; and the like.

  The polyether polyol and the polyester polyol are usually derived from the low molecular weight polyhydric alcohols.

As the polyether polyol derived from the low molecular polyhydric alcohols, at least one selected from the compounds exemplified above as the low molecular polyhydric alcohols, ethylene oxide, propylene oxide, butylene oxide (tetramethylene oxide), Examples include polyols obtained by adding at least one selected from alkylene oxides such as tetrahydrofuran and styrene oxides.
Specific examples of such a polyether polyol include polyethylene glycol and polypropylene glycol (PPG).

Similarly, as the polyester polyol derived from the above low molecular polyhydric alcohols, a condensate (condensation system) of at least one compound selected from the compounds exemplified above as low molecular polyhydric alcohols and a polybasic carboxylic acid is used. Polyester polyol); polycarbonate polyol; and the like.
Specific examples of the polybasic carboxylic acid that forms the condensed polyester polyol include glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, Examples include hydroxycarboxylic acids such as terephthalic acid, isophthalic acid, dimer acid, pyromellitic acid, other low-molecular carboxylic acids, oligomeric acids, castor oil, and a reaction product of castor oil and ethylene glycol (or propylene glycol). . Specific examples of the lactone-based polyol include ring-opening polymers such as propionlactone and valerolactone.

  In the present invention, the various polyol compounds exemplified above may be used alone or in combination of two or more.

In the present invention, as described above, the urethane prepolymer (C) is obtained by reacting a polyol compound with excess HDI. Specific examples thereof include various polyols exemplified above. The thing by the combination of a compound and HDI is mentioned.
Among these, the urethane prepolymer (C) has a polyether structure in the main chain, the urethane polymer (C) is synthesized with a low viscosity, and the sealing material composition of the present invention containing this is prepared. It is preferable for reasons such as having flexibility.
Therefore, it is preferable to use a polyether polyol as the raw material polyol compound of the urethane prepolymer (C). Specifically, it is preferable to use PPG for the reason of being economical.

  Furthermore, in the present invention, the urethane prepolymer (C) comprises an NCO group in the urethane prepolymer (C), an SH group in the polysulfide polyether polymer (A), and the hydroxyl group-containing acrylic polymer (B). It is preferable that the ratio (NCO / (OH + SH)) of the total of OH groups in it is 0.7 to 3.0, more preferably 1.0 to 1.3. preferable. When the content ratio is within this range, the obtained cured product made of the sealing material composition of the present invention becomes a sufficient elastic body.

<Liquid hindered phenol (D)>
As the liquid hindered phenol (D) used in the sealing material composition of the present invention, a liquid hindered phenol can be used at room temperature.
Specific examples of the liquid hindered phenol (D) include 4,6-bis (octylthiomethyl) -o-cresol represented by the following structural formula (1) and (α-methylbenzyl) phenol. Benzenepropanoic acid-3,5-bis (1,1-dimethylethyl) -4-hydroxyalkyl ester represented by the following structural formula (2), and the like, More than one species may be used in combination.

  Commercially available products can be used as the liquid hindered phenol (D), and specific examples thereof include IRGANOX 1520L and IRGANOX 1135 manufactured by Ciba Specialty Chemicals used in the examples.

  By using such a liquid hindered phenol (D), the hydrolysis resistance of the obtained sealing material composition of the present invention can be made better.

  In this invention, content of the said liquid hindered phenol (D) is 0.5-3 mass parts with respect to a total of 100 mass parts of the said polysulfide polyether polymer (A) and a hydroxyl-containing acrylic polymer (B). It is preferable that it is 1 to 2 parts by mass. When the content range is within this range, the hydrolysis resistance of the obtained sealing material composition of the present invention can be further improved.

In one preferred embodiment, the sealing material composition of the present invention contains an epoxy hexahydrophthalic acid diester plasticizer.
Specific examples of the epoxy hexahydrophthalic acid diester plasticizer include, for example, epoxy hexahydrophthalic acid di (2-ethylhexyl), epoxy hexahydrophthalic acid di (n-octyl), and epoxy hexahydrophthalic acid di ( Epoxystearyl) and the like. These may be used alone or in combination of two or more.
In addition, commercially available products can be used as the epoxy hexahydrophthalic acid diester plasticizer, and specific examples thereof include Sansizer E-PS, nE-PS, E- manufactured by Shin Nippon Chemical Co., Ltd. used in the examples. PO etc. are mentioned.
By including such an epoxyhexahydrophthalic acid diester plasticizer, the resulting sealant composition of the present invention has better hydrolysis resistance.

  The sealing material composition of the present invention can contain calcium carbonate from the viewpoint of improving workability and adjusting physical properties after curing.

The calcium carbonate used in the present invention is not particularly limited, and examples thereof include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), colloidal calcium carbonate, and the like.
Moreover, the surface treatment calcium carbonate surface-treated with a fatty acid, a resin acid, a fatty acid ester, a higher alcohol addition isocyanate compound, etc. can also be used.
Specifically, Ryton A-4 (manufactured by Bihoku Flour Chemical Co., Ltd.) is preferably exemplified as the heavy calcium carbonate, and Neocold SPT (manufactured by Takehara Chemical Industry Co., Ltd.), Hakuhika CCR-S as colloidal calcium carbonate. (Shiraishi Kogyo Co., Ltd.) is preferably exemplified.
In addition, as the calcium carbonate surface-treated with fatty acid, whiten 305 (heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), white glaze CCR (collar calcium carbonate, manufactured by Shiroishi Kogyo Co., Ltd.), Calfine 200 (collar calcium carbonate, Maruo) Calcium carbonate surface-treated with a fatty acid ester is preferable. Snowlite SS (heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd.), Sealet 200 (gelatin calcium carbonate, manufactured by Maruo Calcium Co., Ltd.) Etc. are preferably exemplified.
These may be used alone or in combination of two or more.

  The content of calcium carbonate is preferably 100 to 400 parts by mass, and 150 to 300 parts by mass with respect to a total of 100 parts by mass of the polysulfide polyether polymer (A) and the hydroxyl group-containing acrylic polymer (B). More preferably, it is part.

  The sealing material composition of the present invention can contain various additives as required in addition to the above-mentioned various components within a range not impairing the object of the present invention. Examples of additives include fillers other than calcium carbonate, plasticizers other than epoxyhexahydrophthalic acid diester plasticizers, softeners, adhesion promoters, pigments (dyes), anti-aging agents, antioxidants, and antistatic agents. Agents, flame retardants, stabilizers, solvents and the like.

  As fillers other than calcium carbonate, those having various shapes can be used. Specifically, for example, organic or inorganic fillers such as wax stone clay, kaolin clay, calcined clay; fumed silica, calcined silica, precipitated silica, ground silica, fused silica; graphite, metal powder, talc, zeolite, silica Soil; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; magnesium carbonate, zinc carbonate; organic or inorganic filler such as carbon black; vinyl chloride paste resin; glass balloon, acrylonitrile resin balloon; Resin acid, fatty acid ester processed product, fatty acid ester urethane compound processed product may be mentioned.

Specific examples of the plasticizer or softener include, for example, diisononyl phthalate (DINP), dioctyl phthalate, dibutyl phthalate, dibenzyl phthalate; dioctyl adipate, isodecyl succinate; diethylene glycol dipenzoate, pentaerythritol Esters: butyl oleate, methyl acetylricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol polyester adipate, butylene glycol polyester adipate; petroleum-based softeners such as paraffinic oil, naphthenic oil, and aroma oil It is done.
The content of such a plasticizer or softener is preferably 80 parts by mass or less with respect to 100 parts by mass in total of the polysulfide polyether polymer (A) and the hydroxyl group-containing acrylic polymer (B). , 60 parts by mass or less is more preferable.

  Examples of the adhesion imparting agent include a silane coupling agent.

  Specific examples of the silane coupling agent include amino silane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, and mixtures or reactants thereof.

  Here, the aminosilane is not particularly limited as long as it is a compound having an amino group or imino group and a hydrolyzable silicon-containing group. Specific examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy. Silane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2 -(Ami Ethyl) -3-aminopropyl ethyldiethoxysilane and the like.

Specific examples of vinylsilane include vinyltrimethoxysilane, vinyltriethoxysilane, and tris- (2-methoxyethoxy) vinylsilane.
Specific examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4- Epoxycyclohexyl) ethylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
Specific examples of methacrylic silane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Can be mentioned.
Specific examples of the isocyanate silane include isocyanate propyltriethoxysilane.
Specific examples of the ketimine silane include ketiminated propyltrimethoxysilane.

  The content of such an adhesion-imparting agent is 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the polysulfide polyether polymer (A) and the hydroxyl group-containing acrylic polymer (B). preferable.

  Specific examples of pigments (dyes) include inorganic substances such as titanium dioxide, titanium white, zinc oxide, carbon black, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate. Pigments; organic pigments such as azo pigments and copper phthalocyanine pigments.

Specific examples of the anti-aging agent include hindered phenol compounds and hindered amine compounds.
Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Specific examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Specific examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.
Examples of the stabilizer include hindered phenol compounds and triazole compounds.

  Specific examples of the solvent include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and octane; petroleum solvents (for example, mineral spirits) ranging from gasoline to kerosene fractions. Ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether esters such as cellosolve acetate and butylcellosolve acetate;

  In the sealing material composition of the present invention, these various additives can be used in appropriate combination.

  The method for producing the sealing material composition of the present invention is not particularly limited, but the polysulfide polyether polymer (A), the hydroxyl group-containing acrylic polymer (B), the liquid hindered phenol (D), and optionally added. The above-mentioned various additives are mixed by a roll, kneader, extruder, universal agitator, etc. to prepare a base material component, similarly, a urethane prepolymer (C) is prepared as a curing agent component, and these components are used in the field at the time of use. And the like.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<HDI prepolymer (urethane prepolymer C1)>
Urethane synthesized by mixing HDI with bifunctional polypropylene glycol and trifunctional polypropylene glycol as HDI prepolymer (urethane prepolymer C1) and reacting at 80 ° C. for 18 hours in a nitrogen stream in the presence of a tin catalyst. A prepolymer (NCO%: 2.4%) was used.

<XDI prepolymer>
As an XDI prepolymer, a urethane prepolymer (NCO%: synthesized by mixing XDI with bifunctional polypropylene glycol and trifunctional polypropylene glycol and reacting at 80 ° C. in a nitrogen stream in the presence of a tin catalyst for 18 hours. 4.2%) was used.

(Examples 1-7 and Comparative Examples 1-5)
The ingredients shown in Table 1 below are blended in 100 parts by mass of polysulfide polyether polymer A1 (LP-282, manufactured by Toray Fine Chemical Co., Ltd.) with the composition (parts by mass) shown in Table 1, and a universal agitator. To prepare a base material.
The obtained base material was mixed with the HDI prepolymer or XDI prepolymer synthesized above and a color master to obtain a sealing material composition.
About each obtained sealing material composition, the physical property after a standard curing and after heat resistance, and hydrolysis resistance were evaluated as follows. The results are shown in Table 1 below.

<Physical properties after standard curing>
A primer is applied to an aluminum plate, each sealing material composition thus obtained is placed thereon, cured at 23 ° C. for 7 days, and at 50 ° C. for 7 days, 50% modulus (M ₅₀ ) [N / cm of the cured product ² ], breaking strength (T _B ) [N / cm ² ] and breaking elongation (E _B ) [%] were measured at 23 ° C. according to the method described in JIS A1439: 2004.
As the primer, primer No. 45 (manufactured by Yokohama Rubber Co., Ltd.) was used.

<Physical properties after heat resistance>
A primer is applied to an aluminum plate, each sealing material composition thus obtained is placed thereon, cured at 23 ° C. for 7 days, at 50 ° C. for 7 days, and further at 90 ° C. for 14 days, 50% modulus (M ₅₀ ) [N / cm ² ], breaking strength (T _B ) [N / cm ² ] and breaking elongation (E _B ) [%] were measured at 23 ° C. according to the method described in JIS A1439: 2004. did.
As the primer, primer No. 45 (manufactured by Yokohama Rubber Co., Ltd.) was used.

<Hydrolysis resistance>
Put each of the obtained sealing material compositions, put a cured product cured at 23 ° C. for 7 days into a pressure vessel, fill it with distilled water, seal it, heat it at 120 ° C. for 24 hours, and then remove the cured product. It was confirmed that there were no abnormalities such as dissolution and softening.
As a result, the shape before being put in the pressure vessel is retained, and there is elasticity, and the shape that does not change even if touched with a finger is evaluated as `` ○ ''. Even if there was no material attached, the material that deformed was evaluated as “Δ”, and the material that did not retain its shape and adhered to the material when touched with a finger was evaluated as “×”.

The components shown in Table 1 are as follows.
LP282: polysulfide polyether polymer A1, manufactured by Toray Fine Chemical Co., Ltd. UH2000: hydroxyl group-containing acrylic polymer B1, manufactured by Toagosei Co., Ltd. 1520L: liquid hindered phenol D1, manufactured by Ciba Specialty Chemicals Co., Ltd., DINP: plasticizer, Made by J Plus Co., Ltd. ・ Sansocizer E-PS: Epoxyhexahydrophthalic acid diester plasticizer, made by Shin Nippon Rika Co., Ltd. ・ Noxeller TET: Accelerator, Tetraethylene Disulfide, produced by Ouchi Shinsei Chemical Co., Ltd. ・ Neolite SPT: Colloidal Carbonate Calcium, manufactured by Takehara Chemical Industry Co., Ltd. ・ Ryton A-4: Heavy calcium carbonate, manufactured by Bihoku Powder Chemical Co., Ltd. ・ JP333E: Anti-aging agent, Tris (tridecyl) phosphite, manufactured by Johoku Chemical Industry Co., Ltd. ・ Angekor 90N: Physical property adjustment Agent, oleilua Cole, manufactured by Shin Nippon Rika Co., Ltd. ・ Stann-BL: Tin catalyst, di-n-butyltin dilaurate, manufactured by Sansha Kogyo Co., Ltd. ・ Nymene S220: Amine catalyst, polyoxyethylene stearylamine, manufactured by NOF Corporation ・ Color Master: Made by Yokohama Rubber

  As is clear from Table 1, the sealing material compositions obtained in Examples 1 to 7 have a cured product physical property equivalent to or higher than the sealing material compositions obtained in Comparative Examples 1 to 5. And it turned out that all are excellent in hydrolysis resistance. Moreover, it turned out that the sealing material composition obtained in Examples 1-7 does not have a raise of the modulus in the physical property after heat resistance seen in the comparative example 1.

Claims (3)

  Obtained by reaction of polysulfide polyether polymer (A) having two or more thiol groups in one molecule, hydroxyl-containing acrylic polymer (B), hexamethylene diisocyanate and polyol compound, two in one molecule The sealing material composition containing the urethane prepolymer (C) which has the above isocyanate groups, and a liquid hindered phenol (D).   Content of the said hydroxyl-containing acrylic polymer (B) is 5-40 mass parts with respect to a total of 100 mass parts of the said polysulfide polyether polymer (A) and the said hydroxyl-containing acrylic polymer (B), Item 2. A sealing material composition according to Item 1. The sealing material composition according to claim 1 or 2, wherein the liquid hindered phenol (D) is 4,6-bis (octylthiomethyl) -o-cresol represented by the following structural formula.