JP2002188080A - Sealing material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing material composition having excellent weather resistance, stain resistance, water-resistant adhesion and heat resistance. SOLUTION: This sealing composition is characterized in that the composition contains (b) 10-300 pts.wt. filler based on (a) 100 pts.wt. acrylic ester copolymer containing 5-70 wt.% (meth)acrylic ester monomer unit having a cyclohexyl structure at the ester part based on the whole amount of the constituting units, having a reactive group reactable with a cross-linking agent or a self-cross- linkable reactive group at least at one terminal of the polymer, and further having <=10 deg.C glass transition temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealing material composition, and more particularly, to a sealing material composition having excellent weather resistance, stain resistance, water resistance and heat resistance.

[0002]

2. Description of the Related Art Sealing materials are indispensable materials in construction and civil engineering, and as such sealing materials, silicone-based, modified silicone-based, polysulfide-based, polyurethane-based, acrylic urethane-based and the like have been known. I have.

However, for example, denatured silicones,
Polysulfides and polyurethanes have poor weather resistance, silicones have weather resistance but poor pollution, and acrylic urethanes have weather resistance, stain resistance, water resistance, and tensile properties after heat test. , Specifically 50%
Insufficient modulus, strength, elongation,
Each sealant has problems.

[0004] In order to solve such a problem and obtain a sealing material satisfying physical properties required for practical use, various improvements have conventionally been made. For example, in an acrylic urethane-based sealing material, a means of introducing a hydroxyl group into a molecular terminal of an acrylic polymer has been adopted to improve the stain resistance (Japanese Patent Laid-Open No. 7-10957).
Simply by introducing a hydroxyl group at the molecular end,
The performance is just one step. Therefore, conventionally, there has been a demand for the development of a sealing material which is excellent in weather resistance, stain resistance, water adhesion and heat resistance and satisfies physical properties required for practical use.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a sealing material composition having excellent weather resistance, stain resistance, water-resistant adhesiveness and heat resistance. .

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, as an acrylate monomer, a (meth) acrylate monomer having a cyclohexyl structure in an ester portion has been obtained. By using a (meth) acrylic acid ester copolymer having a body unit in a predetermined ratio and having at least one terminal of the polymer having a reactive group capable of reacting with a crosslinking agent or a reactive group capable of self-crosslinking, and a filler. The present inventors have found that it is possible to improve the weather resistance, stain resistance, water resistance and heat resistance of the sealing material, and have completed the present invention.

[0007] The sealing material composition according to claim 1 is
(A) a (meth) acrylic acid ester monomer unit having a cyclohexyl structure in the ester portion in a proportion of 5 to 70% by mass based on the total amount of all constituent units, and at least at one end of the polymer (Meth) acrylate copolymer having a reactive group that reacts with a crosslinking agent or a reactive group capable of self-crosslinking (hereinafter referred to as “(a) (meth) acrylate copolymer”), and ( b) characterized by containing a filler. In this specification, “(meth) acrylic acid” means acrylic acid and / or methacrylic acid, and “(meth) acrylic acid ester”
Acrylic ester and / or methacrylic ester are meant.

The "(a) (meth) acrylate copolymer" is mainly composed of a (meth) acrylate monomer unit having a (meth) acrylate monomer unit as a main constituent unit and a cyclohexyl structure in the ester portion. Monomer unit (hereinafter referred to as “weather-resistant monomer”). By containing such a “weather-resistant monomer” unit as a constituent unit, weather resistance can be imparted. The “weatherproof monomer” is not particularly limited as long as it has a cyclohexyl structure in the ester portion.
Cyclohexyl (meth) acrylate, 4-methylcyclohexyl (meth) acrylate, 4- (meth) acrylic acid
Methoxycyclohexyl, (meth) acrylic acid 4-te
Examples thereof include rt-butylcyclohexyl, isobornyl (meth) acrylate, tricyclodecynyl (meth) acrylate, dicyclodecanyl (meth) acrylate, and adamantyl (meth) acrylate. Among these, acrylate monomers are preferred because they can easily lower the glass transition temperature (hereinafter, referred to as “Tg”) of the copolymer, and cyclohexyl acrylate is particularly preferred for its copolymerizability with other monomers. It is preferable because it is excellent.

The content of the “weatherproof monomer” unit in the “(a) (meth) acrylate copolymer” is usually 5 to 70% by mass based on the total amount of all the constituent units. Preferably 10 to 60% by mass, more preferably 15% by mass.
５０50% by mass. When the content of the “weather-resistant monomer” unit is less than 5% by mass, sufficient weather resistance and stain resistance cannot be imparted to the “(a) (meth) acrylate copolymer”. If the content exceeds 70% by mass, the Tg of the above-mentioned “(a) (meth) acrylate copolymer” becomes high, resulting in poor workability when used as a sealing material composition. .

[0010] The monomer (hereinafter referred to as "other monomer") other than the above "weatherproof monomer" unit contained in the above "(a) (meth) acrylate copolymer" is described below. There is no particular limitation as long as the object of the present invention can be achieved,
It can be various. As the “other monomer”, for example, an acrylate monomer other than the “weatherproof monomer” (hereinafter, referred to as “other acrylate monomer”) can be used. . The “other acrylate monomer” is not particularly limited, but includes an alkyl acrylate having an alkyl group having 2 to 20 carbon atoms and an acryl containing an oxygen atom, a nitrogen atom, a halogen atom, or the like in an ester portion. Acid esters are exemplified. Specifically, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate,
Alkyl acrylates such as neopentyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, lauryl acrylate, tridecyl acrylate and stearyl acrylate, 2-methoxyethyl acrylate, dimethylaminoethyl acrylate, chloroethyl acrylate and acryl Heteroatom-containing acrylates such as trifluoroethyl acid. Among them, an acrylate monomer in which the ester portion is an alkyl group having 4 to 12 carbon atoms is preferable because of its low Tg and excellent weather resistance, and particularly, butyl acrylate and acrylic acid 2 -Ethylhexyl and lauryl acrylate are preferred. In addition, the above "other acrylic acid ester monomers"
May be used alone or in combination of two or more.

The content of the “other acrylate monomer” unit is not particularly limited, but is usually 20 to 90% by mass based on the total amount of all monomer units.
Preferably it is 30-80 mass%. By setting the ratio of the “other acrylate monomer” in the above range, the Tg of the copolymer is reduced, rubber elasticity is further improved, and excellent water resistance and adhesion are preferred.

The above "other monomer" may be used together with or in place of the above "other acrylate monomer", if desired, with another monomer (hereinafter, referred to as "desired monomer"). ) Can be used. Specific examples of the above-mentioned “desired monomer” include, for example, (1) methacrylates (ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate) And (2) crotonic esters (such as ethyl crotonate, butyl crotonate and cyclohexyl crotonate), and (3) α-olefins (ethylene, propylene, 1- (4) chloroethylenes (such as vinyl chloride and vinylidene chloride), (5)
Fluoroethylenes (such as tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene and vinylidene fluoride), (6) vinyl ethers (such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether isobutyl vinyl ether and cyclohexyl vinyl ether), and (7) vinyl esters (Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, veova 9 and veova 10 (manufactured by Shell Chemical Co., fatty acid vinyl having 9 and 10 carbon atoms)) and vinyl laurate, etc. ) Allyl ethers (such as ethyl allyl ether and butyl allyl ether),
(9) isopropenyl ethers, (10) isopropenyl esters, and (11) allyl esters. The “desired monomer” may be one kind,
Two or more kinds may be used in combination.

The content of the "desired monomer" unit is not particularly limited, but is usually 0 to 30% by mass, preferably 0 to 25% by mass, based on the total amount of all the monomer units.
More preferably, it is 0 to 30% by mass. By setting the ratio of the “desired monomer” in the above range, the “(a)
The (meth) acrylate copolymer is preferable because the weather resistance of the copolymer can be further improved.

Further, in addition to the above monomers, a monomer having an ultraviolet absorbing ability, a monomer having photostability, and a monomer having various functional groups can be used. Examples of the monomer having an ultraviolet absorbing ability include 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole and methacryloxyhydroxypropyl-3- [3- (2H-benzotriazole -2-yl)
-5-tert-butyl-4-hydroxyphenyl]
And propionate and 2-hydroxy-4- (methacryloxyethoxy) benzophenone. Also,
1,2,2,6,6
-Pentamethyl-4-piperidyl methacrylate and 2,2,6,6-tetramethyl-4-piperidyl methacrylate. Examples of the functional group-containing monomer include glycidyl acrylate, glycidyl methacrylate and vinyl glycidyl ether; acrylic acid and methacrylic acid; acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N, N-diethyl Acrylamide, methacrylamide, N-methylmethacrylamide, N, N-dimethylmethacrylamide and the like can be mentioned.

The reactive group reactive with the crosslinking agent or the reactive group capable of self-crosslinking in the above-mentioned “(a) (meth) acrylate copolymer” is a reactive group reactive with the crosslinking agent during polymerization or capable of self-crosslinking. It can be produced by using a chain transfer agent having a reactive group. Examples of the chain transfer agent include (1) hydroxyl-containing mercaptans (such as mercaptoethanol, mercaptopropanol, thioglycerol, thiodiethylene glycol and dithioerythritol), and (2) hydroxyl-containing sulfides (hydroxymethyl disulfide, hydroxymethyl trisulfide). , Hydroxyethyl disulfide, hydroxybutyl disulfide, and hydroxyoctyl tetrasulfide), (3) polyfunctional alcohols (such as ethylene glycol, propylene glycol, butanediol and diethylene glycol), and (4) hydrogen peroxide. Examples of the chain transfer agent having a reactive group capable of self-crosslinking include, for example, mercaptosilanes (γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane, etc.) Sulfide silanes (KBM836 manufactured by Shin-Etsu Chemical [special silane coupling agent having a polysulfide structure in the molecule]) and the like. The amount of the chain transfer agent to be used is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the monomer. When the content is within such a range, the molecular weight of the “(a) (meth) acrylate copolymer” in the present invention can be controlled within a preferred range.

The above-mentioned “(a) (meth) acrylate copolymer” is a reactive group present at least at the terminal of the copolymer or a self-crosslinking reactive group after being applied as a component of the sealing material composition. Must be crosslinked by reacting with a crosslinking agent or by self-crosslinking. In order to ensure such a crosslinking reaction, for example, a monomer having a reactive group that reacts with a crosslinking agent or a reactive group that undergoes self-crosslinking (hereinafter, referred to as a monomer having a reactive group)
"Reactive monomers") can be copolymerized.
In this case, the above “(a)” of the above “reactive monomer” unit
The content in the (meth) acrylate copolymer is usually 20% by mass or less, preferably 1 to 15% by mass,
More preferably, it is 2 to 10% by mass. By setting the proportion of the `` reactive monomer '' unit to the above range, the crosslinking of the copolymer becomes sufficient and the copolymer can be sufficiently cured, and the crosslinking density becomes too high and the flexibility is lowered. This is preferable since this can be prevented. In this case, it is preferable that the reactive group present at the terminal of the “(a) (meth) acrylate copolymer” and the reactive group contained in the “reactive monomer” are the same.

When a polyisocyanate is used as a crosslinking agent, a hydroxyl group is preferred as the "reactive group which reacts with the crosslinking agent". Examples of the “reactive monomer” that provides such a hydroxyl group to the “(a) (meth) acrylate copolymer” include hydroxyalkyl acrylates (hydroxyethyl acrylate, hydroxybutyl acrylate, acryl acrylate). Hydroxypropyl acrylate, ε-caprolactone addition product of hydroxyethyl acrylate and pentaerythritol triacrylate, etc., hydroxyalkyl methacrylates (hydroxyethyl methacrylate and hydroxybutyl methacrylate, etc.), hydroxyalkyl vinyl ethers (hydroxyethyl vinyl ether) , Hydroxybutyl vinyl ether and hydroxypropyl vinyl ether) allyl ethers containing hydroxyl groups (hydroxyethyl allyl ether and hydroxybutyl allyl ether, etc.) , Crotonic acid hydroxyalkyl ethers (hydroxyethyl crotonate ethyl and crotonic acid hydroxypropyl, etc.) and the like. Among these, hydroxyethyl acrylate, hydroxybutyl acrylate and hydroxyethyl acrylate and ε-caprolactone addition reaction product are preferred from the viewpoint of low Tg and reactivity with the curing agent, and particularly preferred is hydroxyethyl acrylate. .

When a crosslinking agent is not used in combination,
“(A) (meth) acrylate copolymer” is self-
It has a reactive group capable of crosslinking (hereinafter referred to as “self-crosslinkable group”).
It is necessary to. Such "self-crosslinkable groups"
The acrylic acid ester copolymers self-crosslink
There is no particular limitation as long as it is a reactive group.
Functional group-containing silyl group and isocyanate group.
You. Then, the hydrolyzable group-containing silyl group is
Given to "(a) (meth) acrylate copolymer"
The above “reactive monomer” generally has the following chemical formula
Can be represented by R¹-SiR^Two _nY¹ _(3-n)  (Where n is an integer from 0 to 2, R¹Is olefinic
A group having a saturated bond, R^TwoHas no olefinic bond
An alkyl group having 1 to 20 carbon atoms, Y¹Is a halogen atom,
Lucoxy, acyloxy, phenoxy, mercapto
Group, amino group, iminooxy group or alkenyloxy group
Hydrolyzable groups such as R^TwoAnd Y¹Coefficient
When ([n], [3-n]) is 2 or more, each R^TwoOr Y¹
Each may be the same or different. )

Specific examples of the above-mentioned "reactive monomer" which provides the above-mentioned "(a) (meth) acrylate copolymer" with the above-mentioned hydrolyzable group-containing silyl group include:
(1) vinylsilanes (vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethoxydimethylsilane, vinyltrichlorosilane, etc.), (2) silyl group-containing acrylates trimethoxysilylpropyl acrylate, acrylic (3) silyl group-containing methacrylates (such as trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate and methyldimethoxysilylpropyl methacrylate),
(4) Silyl group-containing vinyl ethers (such as trimethoxysilylpropyl vinyl ether) and (5) silyl group-containing vinyl esters (such as vinyl trimethoxysilylundecanoate). Among them, it is preferable to use vinyl silane or silyl group-containing acrylate having a methoxy group or an ethoxy group from the viewpoint of copolymerizability with the alkyl acrylate and flexibility of the copolymer.

Further, the above-mentioned hydroxyl group is converted to the above-mentioned “(a) (meth)
Reacting the "reactive monomer" given to the "acrylate copolymer" with a compound having two isocyanate groups (for example, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, etc.) The isocyanate group-containing monomer obtained by the above method can also be used as the “reactive monomer”. Further, in order to introduce an isocyanate group or a hydrolyzable group-containing silyl group into the “(a) (meth) acrylate copolymer”, besides using the above-mentioned monomer, for example, a hydroxyl group-containing acrylic A method of reacting a compound having both a hydrolyzable group-containing silyl group such as γ-trimethoxysilylpropyl isocyanate and an isocyanate group with the acid ester copolymer can also be employed.

[0021] In the sealing material composition according to the first aspect,
The above “(a) (meth) acrylate copolymer”
And a more reactive polyalkylene oxide (preferably polypropylene oxide).
The reactive polyalkylene oxide and the above “(a)
The polymer obtained by using the (meth) acrylate copolymer in combination with the (meth) acrylate copolymer copolymer is preferable because the tensile properties (elongation) of the sealing material can be improved.
In this case, the “(a) (meth) acrylate copolymer” and the reactive polyalkylene oxide weight ratio are usually (90 to 30): (10 to 70), preferably (80 to 40). : (20 to 60).

When the above-mentioned “(a) (meth) acrylate copolymer” has a hydrolyzable group-containing silyl group, the hydrolyzable group-containing silyl group other than the acrylate ester copolymer may be used. Can be used in combination. Such polymers are not particularly limited, but those having a silyl group at the terminal of polyalkylene oxide are preferable from the viewpoint of improving tensile properties. Those having a silyl group at the terminal of polypropylene glycol are more preferred, and specific examples include “MS Polymer” (trade name, manufactured by Kaneka Chemical Co., Ltd.) and “Exester” (trade name, manufactured by Asahi Glass).

Further, when the above-mentioned "(a) (meth) acrylate copolymer" has an isocyanate group obtained by reacting a hydroxyl group with one of diisocyanates, a polymer having another isocyanate group is blended. be able to. As such a polymer, a polymer having an isocyanate group at a terminal of a polyalkylene oxide is preferable.

[0024] The method for producing the above-mentioned "(a) (meth) acrylate copolymer" is not particularly limited, and it is produced by ordinary radical polymerization. In this radical polymerization, a radical polymerization initiator can be used. As such a radical polymerization initiator,
Peroxides such as diisopropylperoxydicarbonate, di-2-ethoxyethyloxydicarbonate, and tert-butylperoxypivalate, 2,2′-
Azo compounds such as azobisisobutyronitrile and 2,2′-azobis (2-methylbutyronitrile), and hydrogen peroxide can be used. The amount of the radical polymerization initiator used is preferably 2 parts by weight or less per 100 parts by weight of the monomer, from the viewpoint of making the above-mentioned chain transfer agent work effectively. Further, when using a peroxide or hydrogen peroxide as a radical polymerization initiator, as a decomposition accelerator, a sulfonic acid compound such as benzenesulfonic acid, an inorganic acid such as hydrochloric acid, an onium salt such as triethylbenzylammonium chloride,
Heterocyclic amines such as pyridine can also be used.

The polymerization can be carried out by either solution polymerization using a polymerization solvent or bulk polymerization performed without a solvent. When a polymerization solvent is used, the solvent is not particularly limited as long as polymerization can be performed. Examples thereof include (1) cyclic ethers (such as tetrahydrofuran and dioxane) and (2) aromatic hydrocarbon compounds (benzene, toluene and Xylene, etc.), (3) esters (ethyl acetate, butyl acetate, ethyl ethoxypropionate, etc.), (4) ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), and (5) alcohols (methanol, ethanol, isopropanol and Butanol and the like can be suitably used. The polymerization temperature in the above polymerization is usually 30 to 200 ° C., preferably 50 to 150 ° C., and the polymerization pressure can be from normal pressure to about 5.0 MPa. Further, as a method of adding the monomers, all the monomers may be initially charged in a batch, or semi-batch polymerization in which some of the monomers are sequentially or continuously added as the polymerization proceeds, or continuous polymerization. Good.

The "(a) (meth) acrylate copolymer" is not particularly limited in its physical properties as long as it has the above-mentioned constitution, and may be various as required. Specifically, for example, as described in claim 2, the glass transition temperature (hereinafter, referred to as “Tg”) can be -10 ° C or lower, preferably -20 ° C or lower. Tg
-10 ° C. or lower is preferable because a sealing material composition having excellent rubber elasticity even in winter and having excellent workability can be obtained. The number average molecular weight (in terms of polystyrene) of the above “(a) (meth) acrylate copolymer” determined by gel permeation chromatography (GPC) is usually 10%.
00 to 50000, preferably 2000 to 30000,
More preferably, it can be 3000-10000. By setting the number average molecular weight in the above range, it is possible to provide a sufficient weather resistance to the copolymer and to maintain a suitable viscosity, so that a sealing material composition excellent in workability can be obtained. preferable.

[0027] In the sealing material composition according to claim 1,
In addition to the above “(a) (meth) acrylate copolymer”, the above-mentioned “(b) filler” described below is contained as an essential component. By adding the above-mentioned "(b) filler", the resulting sealing material composition has improved mechanical properties and improved strength and elongation. The above “(b) filler”
Is not particularly limited as long as it does not deteriorate the above-mentioned “(a) (meth) acrylate copolymer” in the present invention. For example, light calcium carbonate, heavy calcium carbonate, titanium oxide, zinc oxide, Carbon black, synthetic silicic acid, talc, zeolite, mica, silica, calcined clay, kaolin, bentonite, aluminum hydroxide and barium sulfate, among which light calcium carbonate, heavy calcium carbonate and titanium oxide are: It is preferable because the effect of improving the properties of the sealing material composition is high. When light calcium carbonate and heavy calcium carbonate are used, the average particle size is not particularly limited, but is in the range of 0.02 to 2.0 μm for light calcium carbonate and 1.0 to 5.0 μm for heavy calcium carbonate. Then
It is preferable because of good miscibility with the above-mentioned “(a) (meth) acrylate copolymer” in the present invention. The “(b) filler” may be only one kind, or two or more different kinds may be used in combination.

The content of the "(b) filler" is not particularly limited, but is usually in the range of 10 to 30 per 100 parts by mass of the acrylate copolymer.
0 parts by mass, preferably 20 to 250 parts by mass, more preferably 50 to 200 parts by mass. The above “(b) filler”
Is more preferable when the content is within the above range, because more excellent mechanical properties are maintained.

In the sealing material composition of the present invention, a catalyst for accelerating the crosslinking reaction can be added in addition to the above-mentioned components. The addition of such a catalyst is preferable because the time required from application of the sealing material composition to crosslinking and curing can be reduced. Examples of the catalyst include organic tin compounds (dibutyltin dilaurate, dibutyltin mercaptide,
Dibutyltin thiocarboxylate, dibutyltin dimaleate, dibutyltin diacetate, dibutyltin diacetacetonate, tin octylate, dioctyltin dimaleate, etc., organic lead compounds (lead octenoate, lead octylate, etc.), organic titanium compounds ( Tetrabutyl titanate, tetrapropyl titanate, etc.), amine compounds (triethylamine, N, N-dimethylcyclohexylamine,
N, N, N'N'-tetramethylethylenediamine, triethylenediamine, N, N'-dimethylpiperazine,
N-methylmorpholine and diazabicycloundecene). Among them, organic tin compounds are preferable because of their excellent reactivity. The preferred content of the catalyst is 0.01 to 10% by mass, and preferably 0.1 to 0.5% by mass, based on the “(a) (meth) acrylate copolymer”. By setting the content in such a range, it is possible to impart curability having appropriate workability and appropriate pot life to the sealant composition of the present invention.

In the sealing material composition of the present invention, in addition to the above-mentioned components, various additives can be appropriately added as needed as long as the object of the present invention is not impaired. Examples of such additives include ultraviolet absorbers (benzophenone-based compounds, benzotriazole-based compounds, oxalic anilide-based compounds, etc.), light stabilizers (hindered amine-based compounds, etc.), antioxidants (hindered phenol-based compounds, etc.). ), Plasticizers (dioctyl phthalate, diisononyl phthalate, dioctyl adipate, chlorinated paraffin, epoxidized soybean oil, polyalkylene glycol compounds, etc.), adhesion enhancers, anti-sagging agents (hydrogenated castor oil, etc.), dehydrating agents (orthoformic acid) Methyl and methyl orthoacetate), coloring agents and organic solvents. Further, after the sealing material composition of the present invention is cured, an anti-tack agent (a photo-curable composition composed of polyester polyacrylate, etc., tung oil, linseed oil, polybutadiene, unsaturated polyester, etc.) Curable compound).

In the sealing material composition of the present invention, when the “reactive group that reacts with the crosslinking agent or the self-crosslinkable reactive group” in the “(a) (meth) acrylate copolymer” is a hydroxyl group, It is necessary to use a curing agent.
Suitable examples of such a curing agent include a polyvalent isocyanate compound, a polyvalent blocked isocyanate compound, and an aminoplast resin. Specifically, for example, polyvalent isocyanate compounds include 1,6-hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, and xylylene diisocyanate. In addition, polyisocyanate compounds such as isocyanurate compounds, biuret compounds, and polyol-modified compounds are exemplified. Examples of the blocking agent for the polyvalent blocked isocyanate compound include phenols, oximes, and alcohols. Among these, a polyvalent isocyanate is preferable because it can be cured at room temperature, and a polyoxyalkylene-modified isocyanate is more preferable because the obtained sealing material can be softened. In this case, it is particularly preferable that the polyoxyalkylene is a polyoxypropylene whose main chain skeleton may be partially polyoxyethylene.

When a polyvalent isocyanate compound is used as a curing agent, the amount of the polyvalent isocyanate to be added to the above-mentioned (a) (meth) acrylic acid ester copolymer is preferably the amount of the above-mentioned (a) (meth) acrylic The ratio of the number of moles of hydroxyl groups of the “acid ester copolymer” to the number of moles of the polyvalent isocyanate is 1: (0.8 to 1.3), more preferably 1: (0.9 to 1.2). It is.

The sealing material composition of the present invention can improve weather resistance, stain resistance, water adhesion and heat resistance by having the above-mentioned constitution. Specifically, JI
In the tensile adhesion test after immersion in water (substrate: aluminum) in the test method of SA1439 for building sealing materials, the breaking strength was 0.35 MPa or more (preferably 0.4 mm).
0 MPa or more), elongation at break of 250% or more (preferably 270% or more), and 50% tensile stress of 0.04 MPa or more (preferably 0.05 MPa or more). Further, in a 90 ° C. heating test in a test method of a building sealing material according to JIS A1439, a breaking strength of 0.30 MPa or more (preferably 0.35 MPa or more,
More preferably 0.40 MPa or more), and the breaking elongation is 27
The 0% or more (preferably 280% or more) and the 50% tensile stress can be 0.05 MPa or more (preferably 0.08 MPa or more, more preferably 0.10 MPa or more).

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. (1) Synthesis of acrylate copolymer <Synthesis Example 1> 160 g of ethylene glycol and p-toluene were placed in a four-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel, a glass tube for nitrogen replacement, and a stirrer. 3.6 g of sulfonic acid was charged, and the temperature was raised to 130 ° C. while purging with nitrogen. Next, 52.5 g of cyclohexyl acrylate (hereinafter referred to as “CHA”), 52.5 g of butyl acrylate (hereinafter referred to as “BA”), and 6 g of a polymerization initiator (trade name “Perbutyl D” manufactured by NOF CORPORATION) were added in 2 parts. It was dropped over time. Then, the temperature was further raised to 150 ° C. and maintained for 2 hours, and then cooled to 90 ° C.
g was added dropwise to terminate the polymerization. After that, toluene was added to 50
0 g was added for dilution, then the gel component was filtered, and a large amount of water was added to separate the acrylate copolymer. Since the obtained acrylic ester copolymer contained toluene, it was purified by drying under reduced pressure. The yield of the acrylate copolymer was 52%.

<Synthesis Example 2> A four-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel, a glass tube for nitrogen replacement and a stirrer was charged with 300 g of toluene, 3.5 g of mercaptoethanol, 1.0 g of CHA, and 1.0 g of BA. 5 g, 2-ethylhexyl acrylate (hereinafter referred to as "HA")
3.1 g of hydroxyethyl acrylate (hereinafter referred to as “HE
A) and 2 g of 2,2′-azobisisobutyronitrile, and 95 parts of the mixture were blown with nitrogen.
At ℃, the polymerization reaction was started. Thereafter, CHA18.
0 parts, BA 36.0 parts, HA 31.5 parts, HEA 4.5
Part of the solution was continuously dropped over 6 hours to carry out a polymerization reaction. Then, the obtained reaction solution was poured into methanol to separate the acrylate copolymer, and then dried under reduced pressure to obtain an acrylate copolymer having a polymerization rate of 92%.

<Synthesis Example 3> 2-Hydroxyethyl disulfide 150 was placed in a four-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel, a glass tube for purging nitrogen and a stirrer.
g, and the temperature was raised to 100 ° C. while purging with nitrogen.
Then CHA 25.0 g, BA 70.0 g, HEA
5.0 g and 1.5 g of 2,2′-azobisisobutyronitrile were charged and kept at 100 ° C. for 2 hours. After cooling, 100 g of toluene was added for dilution, and the mixture was allowed to stand to remove the lower unreacted 2-hydroxyethyl disulfide.
Next, a large amount of water was added to separate the acrylate copolymer. The resulting acrylate copolymer was purified by drying under reduced pressure because it contained toluene. The yield of the acrylate copolymer was 77%.

<Synthesis Examples 4 to 5 and Comparative Synthesis Examples 1 and 2> An acrylic acid ester copolymer was obtained by using the monomers shown in Table 1 below and performing the same operation as in Synthesis Example 2. Was synthesized. In Table 1, "MPSi" is mercaptopropyltrimethoxysilane, "ME" is mercaptoethanol, "ATS" is acryloxypropyltrimethoxysilane, and "VMS" is vinyltrimethoxysilane. The unit of the number is g.

[0038]

[Table 1]

(2) Physical Properties of Acrylic Ester Copolymer Number average molecular weight (hereinafter referred to as “Mn”) of each acrylate copolymer obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 and 2 above. , Weight average molecular weight (hereinafter referred to as “Mw”), polydispersity, hydroxyl value (hereinafter referred to as “OHV”), and Tg were measured. Mn, Mw and polydispersity were determined by using tetrahydrofuran as a solvent and converting the molecular weight determined by GPC into polystyrene. Tg was determined by DSC measurement. Further, the composition of each copolymer obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 and 2 and the number of functional groups per molecule of the copolymer (in terms of number average molecular weight) were determined by ¹ H-NMR. The results are shown in Table 2 below.

[0040]

[Table 2]

(3) Preparation of Sealing Material and Performance Evaluation Based on 100 parts by weight of the acrylate copolymer obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 and 2, isocyanate-modified polypropylene oxide (manufactured by Takeda Pharmaceutical Co., Ltd.) , Trade name "XL1031T-11"), polypropylene oxide having a hydrolyzable group-containing silyl group (manufactured by Kanebuchi Chemical Co., trade name "Silyl S203"), light calcium carbonate (manufactured by Maruo Calcium, trade name "Calfine 500") ), Heavy calcium carbonate (Shiraishi Kogyo, trade name "Whiteton S")
B "), titanium oxide (trade name" C ", manufactured by Ishihara Sangyo Co., Ltd.)
R-97 "), a plasticizer (dioctyl phthalate), a curing catalyst (dibutyltin dilaurate), and an antioxidant (trade name" Tinuvin B75 "manufactured by Ciba Specialty Chemical Co., Ltd.) in parts by mass shown in Table 3 below. By blending, each sealing material of Examples 1 to 5 and Comparative Examples 1 and 2 was manufactured.

For each of the sealing materials of Examples 1 to 5 and Comparative Examples 1 and 2, JIS A1439, a tensile adhesion test (adherend: aluminum) which is a test method of a sealing material for building, a tensile test after immersion in water An adhesion test and a 90 ° C heating test were performed. The results are shown in Table 3 below. The determination result of the breaking state was represented by CF: cohesive failure of the sealing material, and AF: peeling from the interface.

The above Examples 1 to 5 and Comparative Examples 1 to 2
Each of the sealing materials was subjected to an accelerated weather resistance test and a stain resistance test by the following methods. Table 4 shows the results. Accelerated weathering test: The sample was attached to a holder described in JIS 1439, and the surface state and elongation retention (%) after being put in a sunshine weatherometer (manufactured by Suga Test Instruments) for 4000 hours were measured. Regarding the appearance of the surface state, ○:
No change, Δ: slight cracking, ×: deep cracking. As the elongation retention (%), a value of (elongation after accelerated weathering resistance / initial elongation) × 100 was used. Stain resistance test; upper surface 1 of 7 cm x 15 cm glass plate
/ 2, apply the sample with a spatula so that bubbles do not enter.
mm test plate was prepared. After 8 months of outdoor exposure in Funamicho, Nagoya City, the degree of contamination was visually evaluated according to the following criteria. ：: little dust adhered, △: little dust adhered, ×: considerable dust adhered

[0044]

[Table 3]

(4) Effect of Example From Table 3, it is understood from Table 3 that acrylic ester using cyclohexyl acrylate, which is an acrylic ester having a cyclohexyl structure in the ester portion, is used as the monomer unit of the acrylic ester copolymer. Examples 1 to 5 using copolymers (Synthesis Examples 1 to 5)
The sealing material composition has a breaking strength of 0.43 to 0.52MP even after immersion in water in a tensile adhesion test.
a, Since the elongation at break is as high as 280 to 580%, it is understood that the adhesiveness is excellent in water resistance. In the accelerated weathering test, there was no change in the appearance, and the strength retention was 58 to 72.
% And the elongation retention are as high as 71 to 82%, indicating that they are excellent in weather resistance. Further, in the heat resistance test, the breaking strength was 0.43 to 0.77 MPa and the breaking elongation was 30.
0-640%, 50% tensile stress 0.13-0.15M
Since it is as high as Pa, it is understood that it is excellent in heat resistance and also excellent in stain resistance.

On the other hand, an acrylic ester copolymer in which cyclohexyl acrylate, which is an acrylic ester having a cyclohexyl structure in the ester portion, is not used as a monomer unit of the acrylic ester copolymer (Comparative Synthesis Example) In the tensile adhesion test, the sealing material compositions of Comparative Examples 1 and 2 using 1 and 2) showed almost the same results as the sealing material compositions of Examples 1 to 5 after curing, but water After immersion, the breaking strength is 0.10
0.30 MPa, elongation at break as low as 200 to 230%,
It can be seen that peeling from the interface was caused, and the water-resistant adhesiveness was poor. In the accelerated weather resistance test, cracks were generated and the appearance was inferior to those of the sealing material compositions of Examples 1 to 5, and the strength retention was 23 to 50% and the elongation retention was 25 to 48%. It turns out that it is low and it is inferior to weather resistance. Further, in the heat resistance test, the breaking strength was 0.10 to 0.2.
Since the breaking elongation is 8 MPa, the elongation at break is 150 to 200%, and the 50% tensile stress is as low as 0.01 to 0.02 MPa, the heat resistance is poor and the stain resistance is also poor.

The present invention is not limited to the specific embodiments described above, but may be variously modified within the scope of the present invention according to the purpose and application.

[0048]

According to the present invention, a sealing material composition having excellent weather resistance, stain resistance, water resistance and heat resistance can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4H017 AA24 AA25 AA31 AB01 AB15 AC01 AC05 AD05 AE03 4J002 BG031 BG071 DA037 DE077 DE137 DE147 DE237 DJ007 DJ017 DJ037 DJ047 DJ057 EC077 EN016 EU136 EU236 EZ046 FD017 AL03Q04 AL08Q08 AL03 BA04P BA04Q BA31Q BB01Q BC04P BC07P BC09P CA04 JA05

Claims (4)

[Claims] (A) a (meth) acrylic acid ester monomer unit having a cyclohexyl structure in an ester portion in a proportion of 5 to 70% by mass based on the total amount of all constitutional units, and A sealing material composition comprising a (meth) acrylate copolymer having a reactive group capable of reacting with a crosslinking agent or a reactive group capable of self-crosslinking at one end of a united product, and (b) a filler. 2. The sealing material composition according to claim 1, wherein the (a) (meth) acrylate copolymer has a glass transition temperature of -10 ° C. or lower. 3. The ratio of the (a) (meth) acrylate copolymer to the (b) filler is 100 parts by mass of the (a) (meth) acrylate copolymer. The sealant composition according to claim 1 or 2, wherein the filler is 10 to 300 parts by mass. 4. The sealing material composition according to claim 1, further comprising a catalyst for accelerating a crosslinking reaction.