JP5999464B1 - Wall having joint structure and joint construction method - Google Patents

Abstract

A wall having a joint structure constituted by using a sealing material that has a low modulus change rate after heating and can maintain flexibility, and a joint construction method. A wall having a joint structure of a structure is a second adherend disposed at a position adjacent to the first adherend with a gap between the first adherend and the first adherend. A body 12 and a one-component room temperature moisture-curing sealing material 20 that is filled in a gap through a primer and has a low modulus change rate after heating are provided. [Selection] Figure 1

Description

  The present invention relates to a wall having a joint structure and a joint construction method. In particular, the present invention relates to a wall having a joint structure of a structure such as a building, and a joint construction method.

  Walls using ceramic siding boards or metal siding boards are widely adopted as the walls of structures such as buildings. In particular, the walls made of ceramic siding boards are constructed by filling the joints between the adjacent ceramic siding boards with a backup material and then applying a primer to the sides of the ceramic siding boards and filling the sealing material. The Conventionally, a joint structure of ceramic siding board provided as an outer wall of a building, which has a smooth surface on one side of a long base material made of synthetic resin foam and does not have air permeability The joint material structure of the ceramic siding board in which the back-up material with the layer formed is loaded in the back part of the joint part so that the surface layer side faces the opening side of the joint part, and the joint part is further filled with a low modulus sealing material It is known (for example, see Patent Document 1). According to the joint structure of the ceramic siding board described in Patent Document 1, it is possible to prevent a ridge or an elliptical bulge protruding from the surface of the sealing material in the joint of the building with a simple configuration.

  Furthermore, in the sealing material for construction, for example, a large elongation at break is required so as to cope with the expansion and contraction of the adherend such as the contraction of the ceramic siding board caused by the aging (see, for example, Non-Patent Document 1). .) And since it is thought that the life extension of buildings such as houses is further promoted, it is expected that the sealing material is required to have a long-term durability of 15 years or more, more preferably 30 years or more (for example, Non-patent document 1).

JP-A-10-219960

Architectural Sealing Materials-Basics and Correct Usage-Editorial Committee, "Constructive Sealing Materials-Basics and Correct Usage-", Japan Sealing Materials Industry Association, 1997, 203-212

  The sealant filled in the joints of the walls having joint structures used for the outer walls of structures such as buildings is not only in contact with rainwater but also exposed to a high temperature environment in summer. It is desirable that the sealing material filled in the joint maintains high elongation characteristics and the like even after such heat exposure. However, in the conventional wall structure including Patent Document 1, it is not considered that it is important from the viewpoint of long-term durability to suppress the rate of change in modulus after heat exposure of the sealing material filling the joints. . Further, when a ceramic siding material is used, a sealer is generally applied to the siding material including a small edge surface for the purpose of surface reinforcement. When a ceramic siding material is used as an outer wall material, the ceramic siding material is usually cut on site and attached to the housing, and then a sealer is applied to the small edge that is the cut surface. However, since the adhesive force between the sealer and the siding material is limited, when the modulus of the sealing material is large, peeling or deformation occurs due to an external force such as an earthquake. As a result, the sealer such as the small mouth surface peels off in the water stop structure of the siding material, which may cause water leakage.

  Accordingly, an object of the present invention is to provide a wall having a joint structure constituted by using a sealing material that has a low modulus change rate after heating and can maintain flexibility, and a joint construction method.

In order to achieve the above object, the present invention is a wall having a joint structure of a structure, and is disposed at a position adjacent to each other with a gap between the first adherend and the first adherend. The second adherend to be bonded and the gap filled with a primer, JTC S-0001 Sealing material for ceramic siding Tested according to JTC standards, heating at 80 ° C. for 14 days The modulus after 50% elongation is less than 0.15 N / mm ² and the rate of change in modulus at 50% elongation after heating at 80 ° C. for 14 days is 40% or less, the maximum after heating at 80 ° C. for 14 days. It has a joint structure including a one-component room temperature moisture-curing sealing material having an elongation rate under load of 300% or more and a change rate of elongation rate at the maximum load after heating at 80 ° C. for 14 days being 40% or less. A wall is provided.

  In the wall having the joint structure, the first adherend and the second adherend may be siding materials.

In order to achieve the above object , the present invention is a wall having a joint structure of a structure, and a position adjacent to each other with a gap between the first adherend and the first adherend. A one-part room temperature moisture-curing sealant filled in the gap via a primer, wherein the one-part room temperature moisture-curing sealant is (A1 component) main chain skeleton A polymer composed of butyl acrylate monomer units having a number average molecular weight of 20,000 or more, and (A2 component) a polymer in which the main chain skeleton is an oxyalkylene polymer and has a crosslinkable silicon group at the terminal And (B) a monofunctional epoxy compound, and (C) an alkoxysilane compound that reacts with water to produce an amine compound having at least one alkoxysilyl group in one molecule , (A1 component) And (A2 component) total 100 With respect to the amount unit, it is provided a wall having a joint structure obtained by curing the one-part room temperature moisture curable sealant composition is in the range of 90 parts by mass or less 30 parts by mass or more (A1 component). Further, (A1 component) may be a polymer obtained by reacting at least butyl acrylate with diethyl 2,5-dibromoadipate.

Further, in order to achieve the above object, the present invention provides a first adherend and a second adherend disposed at a position adjacent to each other with a gap between the first adherend and the first adherend. A backup material loading step of loading a backup material into a gap between them, and a primer application step of applying a primer to the surface facing the gap of the first adherend and the surface facing the gap of the second adherend. , After curing the gap on the backup material, JTC S-0001 Sealing material for ceramics siding Judgment test results in accordance with JTC standards, modulus at 50% elongation after heating at 80 ° C. for 14 days Is less than 0.15 N / mm ² , the rate of change in modulus at 50% elongation after heating at 80 ° C. for 14 days is 40% or less, and the elongation rate at maximum load after heating at 80 ° C. for 14 days is 300%. % Or more, 80 ° C Joint construction method and a filling step 04, the maximum load when the elongation rate of change after heating is filled in one pack cold moisture-curable sealant composition 40% or less is provided.

  According to the wall having the joint structure and the joint construction method according to the present invention, the wall having the joint structure constituted by using a sealing material that has a low modulus change rate after heating and can maintain flexibility, and A joint construction method can be provided.

It is sectional drawing of the wall which has the joint structure which concerns on this Embodiment.

[Outline of wall with joint structure]
The wall having a joint structure according to the present embodiment is a wall having a joint structure of a structure including a building such as a house and having a plurality of adherends. A predetermined gap is provided between the plurality of adherends, and a one-component room temperature moisture-curing sealing material with a low modulus change rate after heating is filled in the gap via a primer, so that water immersion or Even when exposed to heat, a wall having a joint structure that can maintain long-term durability of several decades or more while maintaining flexibility without increasing the modulus is formed.

[Details of wall with joint structure]
FIG. 1 shows an example of an outline of a conceptual cross section of a wall having a joint structure according to the present embodiment.

  The wall 1 having a joint structure according to the present embodiment is a second adherend disposed at a position adjacent to the first adherend 10 with a gap between the first adherend 10 and the first adherend 10. A body 12 and a one-pack room temperature moisture-curing sealing material (hereinafter, also referred to as “sealing material 20” or simply “sealing material”) filled in the gap and having a low modulus change rate after heating are provided. The wall 1 having a joint structure includes a primer layer 30 between the first adherend 10 and the sealing material 20 and between the second adherend and the sealing material 20. Further, the wall 1 having the joint structure can be provided with a backup material 40 between the structure (not shown) and the sealing material 20. The one-pack room temperature moisture-curing sealant is formed by curing a one-pack room temperature moisture-curing sealant composition (hereinafter sometimes simply referred to as “sealing material composition”).

(First adherend 10 and second adherend 12)
Specifically, the first adherend 10 and the second adherend 12 are ceramic, metal, wood, and / or resin siding materials. In the present embodiment, the first adherend 10 and the second adherend 12 include, for example, a ceramic plate that mainly includes cement, a fiber raw material, and an admixture, has excellent fire resistance, and can be mass-produced. It is preferable to use a ceramic siding material such as a ceramic plate.

(Sealing material 20)
The sealing material 20 according to the present embodiment is a one-component room temperature moisture-curing sealing material. As a one-component room temperature moisture-curing type sealing material, “NPO Corporation Housing Exterior Technical Center Standard JTC S-0001 Ceramic Siding Sealing Material JTC Standard 2004 (September 1, 2004)” (hereinafter “Siding Sealing”) A sealing material having an initial 50% tensile modulus of less than 0.2 N / mm ² in a tensile adhesion test result tested in accordance with “material standard”) is used. Further, the one-pack room temperature moisture-curing type sealing material is preferably a sealing material having a 50% tensile modulus of less than 0.2 N / mm ² after the heat exposure acceleration test (that is, after heating).

More specifically, as a one-component room temperature moisture curable sealing material, the modulus at 50% elongation after heating is less than 0.2 N / mm ² in the tensile adhesion test result tested in accordance with the standards for sealing materials for siding. The rate of change in modulus at 50% elongation after heating is 40% or less, the rate of elongation at maximum load after heating is 300% or more, and the rate of change in elongation at maximum load after heating is It is preferable to use a sealing material that is 40% or less. Moreover, as a one-component room temperature moisture-curing type sealing material, in a tensile adhesion test result tested in accordance with a siding sealing material standard, the modulus at 50% elongation after heating is less than 0.15 N / mm ² , The rate of change in modulus at 50% elongation after heating is 30% or less, the rate of elongation at maximum load after heating is 400% or more, and the rate of change in elongation at maximum load after heating is 30% or less. It is more preferable to use the sealing material which is.

  The rate of change of the modulus at 50% elongation after heating is the absolute value of the value obtained by subtracting the value of the “modulus at 50% elongation after heating” from the value of “modulus at 50% elongation after heating”. Divide by the value of “modulus at initial 50% elongation” to obtain 100 times. Also, the rate of change of the elongation rate at the maximum load after heating is the absolute value obtained by subtracting the value of the “elongation rate at the initial maximum load” from the value of the “elongation rate at the maximum load after heating”. The value is obtained by dividing the value by the value of “elongation rate at initial maximum load” and multiplying by 100. Here, “initial” refers to the time when a one-component room temperature moisture-curing sealant composition is prepared and the prepared composition is cured.

  For example, as a one-component room temperature moisture curable sealing material composition, (A) a crosslinkable silicon group-containing organic polymer having a number average molecular weight of 15,000 or more and flexibility and / or adhesiveness of a cured product of the composition A sealing material composition containing (B) a monofunctional epoxy compound that secures the above and (C) an alkoxysilane compound that reacts with water to form an amine compound having one alkoxysilyl group is used. The one-pack room temperature moisture-curing sealant is cured by crosslinking of the crosslinkable silicon group at room temperature due to moisture in the air. Therefore, the one-pack room temperature moisture-curing sealant is normally filled in a container that can block moisture from entering so that the performance can be maintained until the user uses it (for example, for one year). Since the one-component moisture-curing sealant composition according to this embodiment can contain a ketiminated aminosilane compound, in this case, even if it is a one-component type, it exhibits excellent storage stability.

(Component A: Crosslinkable silicon group-containing organic polymer)
(A) The crosslinkable silicon group of the crosslinkable silicon group-containing organic polymer is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. As the crosslinkable silicon group, for example, a group represented by the general formula (1) is suitable.

In formula (1), R ¹ represents an organic group. R ¹ is preferably a hydrocarbon group having 1 to 20 carbon atoms. Among these, R ¹ is particularly preferably a methyl group. R ¹ may have a substituent. When two or more R ¹ are present, the plurality of R ¹ may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, the plurality of X may be the same or different. a is an integer of 0, 1, 2, or 3. In order to obtain a sealing material composition having a sufficient curing rate in consideration of curability, a in formula (1) is preferably 2 or more, and more preferably 3. In order to obtain a sealing material composition having sufficient flexibility, a is preferably 2.

  Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.

  The hydrolyzable group represented by X is not particularly limited. Examples thereof include an alkoxy group, an acyloxy group, a ketoximate group, an aminooxy group, and an alkenyloxy group. In these, an alkoxy group is preferable from a viewpoint that hydrolysis property is moderate and it is easy to handle. Among alkoxy groups, a group having a small number of carbon atoms has a higher reactivity, and the reactivity decreases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and application, a methoxy group or an ethoxy group is usually used.

Examples of the crosslinkable silicon group include trialkoxysilyl groups such as a trimethoxysilyl group and a triethoxysilyl group, dialkoxysilyl groups such as —Si (OR) ₃ , a methyldimethoxysilyl group, and a methyldiethoxysilyl group; SiR ¹ (OR) ₂ may be mentioned. Here, R is an alkyl group such as a methyl group or an ethyl group. Moreover, a crosslinkable silicon group may be used by 1 type, or may be used together 2 or more types. The crosslinkable silicon group may be bonded to the main chain, the side chain, or any of them. From the viewpoint of excellent physical properties of the cured product such as tensile properties of the cured product of the sealing material composition, it is preferable that a crosslinkable silicon group is present at the molecular chain terminal. In the organic polymer of component (A), the crosslinkable silicon group is preferably present in an average of 1.0 to 5 in an organic polymer molecule, and preferably 1.1 to 3 in number. More preferred.

  (A) Specific examples of the main chain skeleton of the crosslinkable silicon group-containing organic polymer include polyoxyalkylene polymers such as polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-polyoxypropylene copolymers. ; Hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, polyisoprene, polybutadiene, hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; 2 bases such as adipic acid Polyester polymer obtained by condensation of acid and glycol or ring-opening polymerization of lactones; (meth) acrylic acid ester obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate Polymer: (meth) acrylic acid ester monomer, vinyl acetate, acrylo Vinyl polymer obtained by radical polymerization of monomers such as tolyl and styrene; Graft polymer obtained by polymerizing vinyl monomer in organic polymer; Polysulfide polymer; Polyamide polymer; Polycarbonate polymer A diallyl phthalate polymer and the like. These skeletons may be contained alone in (A) the crosslinkable silicon group-containing organic polymer, or two or more kinds may be contained in blocks or randomly. In the present embodiment, it is preferable to include a telechelic polymer (that is, a polymer substantially having a silyl group as a functional group at both ends) from the viewpoint of improving the elongation characteristics of a sealing material obtained by curing. Here, “substantially” indicates that 50% or more of the main chain skeleton is a polymer having silyl groups at both ends. Therefore, in the telechelic polymer according to the present embodiment, 50% or more of the main chain skeleton includes a polymer having silyl groups at both ends. The telechelic polymer preferably contains 60% or more, more preferably 70% or more, and more preferably 80% or more of the polymer having silyl groups at both ends from the viewpoint of improving elongation properties. Most preferred. In addition, the sealing material obtained by curing contains a predetermined amount of a polymer having a main chain skeleton of butyl (meth) acrylate and having a functional group at the terminal from the viewpoint of exhibiting excellent adhesiveness and maintaining flexibility. Is preferred. Furthermore, from the viewpoint of improving the compatibility of the sealing material composition, the main chain skeleton is composed of a butyl (meth) acrylate monomer unit and a stearyl (meth) acrylate monomer unit, and has a functional group at the terminal. It is also preferable to contain a predetermined amount.

  Furthermore, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers can be obtained with a relatively low glass transition temperature. The cured product is preferable because it is excellent in cold resistance. In addition, polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferable because they have high moisture permeability and are excellent in deep part curability when made into a one-component composition.

Among these, oxyalkylene-based polymers, (meth) acrylic acid ester-based polymers, or mixtures thereof are main chain skeletons from the viewpoint of having large elongation characteristics and small tensile modulus (tensile stress) required for sealing materials. As preferred. In particular, as the tensile modulus of the cured product of the sealing material composition, the initial 50% tensile modulus at a test temperature of 23 ° C. measured in accordance with the standards for sealing materials for siding is less than 0.2 N / mm ^2. preferable. In addition, it is preferable that the 50% tensile modulus prescribed | regulated in JASS8 waterproofing construction (Architectural Institute of Japan) is also a low value. Further, since a sealing material, particularly a sealing material used for construction, is exposed outdoors for a long time, it is preferable that the tensile modulus is maintained even after exposure under adverse conditions. For example, it is preferable that the tensile modulus after the thermal exposure acceleration test does not exceed 0.2 N / mm ² .

The polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the general formula (2).
-R ² -O- ··· ⁽²⁾
In general formula (2), R ² is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and having 2 to 4 carbon atoms. The linear or branched alkylene group is more preferable.

Specific examples of the repeating unit represented by the general formula (2) include
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, _{-CH 2 CH 2 CH 2 CH 2} O- and the like. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, a main chain skeleton composed of a polymer mainly composed of oxypropylene is preferable.

  The molecular weight of the oxyalkylene polymer having a crosslinkable silicon group is preferably a high molecular weight in order to reduce the tensile modulus, which is the initial tensile property of the cured product, and increase the elongation at break. In the present embodiment, the lower limit of the number average molecular weight of the oxyalkylene polymer is preferably 15,000, more preferably 18,000 or more, and more preferably 20,000 or more. As the molecular weight increases, the viscosity of the polymer increases and the viscosity of the sealing material composition also increases. Therefore, a polymer partially including a polymer having a number average molecular weight of 20,000 or more is also preferable. The upper limit of the number average molecular weight is preferably 50,000, and more preferably 40,000. In addition, the number average molecular weight which concerns on this embodiment is a polystyrene conversion molecular weight by gel permeation chromatography. If the number average molecular weight is less than 15,000, the tensile modulus and elongation at break may not be sufficient. If it exceeds 50,000, the viscosity of the composition may increase and workability may be reduced.

  In addition, a (meth) acrylic polymer having a crosslinkable silicon group having a number average molecular weight of 15,000 or more (hereinafter sometimes referred to as A1 component) and a number average molecular weight having a crosslinkable silicon group of 15,000 or more. An oxyalkylene polymer (hereinafter sometimes referred to as A2 component) can be used in combination. From the viewpoint that the sealing material obtained by curing the one-component room temperature moisture curable sealing material composition according to the present embodiment reduces the modulus change rate after heating and increases the elongation rate after heating, the A1 component is 10 mass% or more is preferable with respect to the total amount of A1 component and A2 component, 20 mass% or more is more preferable, and 30 mass% or more is especially preferable.

  If the content of the crosslinkable silicon group in the polyoxyalkylene polymer is moderately reduced, the crosslink density in the cured product will decrease, resulting in a softer cured product in the initial stage, resulting in reduced modulus characteristics and elongation at break. The characteristic becomes large. In the polyoxyalkylene polymer, the number of crosslinkable silicon groups is preferably 1.2 or more and 2.8 or less on average in one molecule of the polymer, and is 1.3 or more and 2.6 or less. More preferably, it is more preferably 1.4 or more and 2.4 or less. When the number of crosslinkable silicon groups contained in the molecule is less than one, the curability is insufficient, and when the number is too large, the network structure becomes too dense to exhibit good mechanical properties. And in the case of a bifunctional polymer whose main chain skeleton is a straight chain, the crosslinkable silicon groups of the polymer should be present in an average of 1.2 or more and less than 1.9 in one molecule of the polymer. Is more preferable, 1.25 or more and 1.8 or less are more preferable, and 1.3 or more and less than 1.7 are more preferable. In particular, in the case of producing a so-called non-plastic blended sealing material composition which does not contain a low molecular weight plasticizer having a molecular weight of 800 or less, and further a molecular weight of 1000 or less, such as a phthalate ester plasticizer, it is crosslinkable. It is preferable that silicon groups are present in an average of 1.2 or more and 1.8 or less, more preferably 1.3 or more and 1.7 or less, in one molecule of the polymer.

  The oxyalkylene polymer having a crosslinkable silicon group may be linear or branched. From the viewpoint of reducing the tensile modulus, the oxyalkylene polymer having a crosslinkable silicon group is preferably a linear polymer. In particular, when producing a non-plastic blending sealant composition, it is preferably linear. The molecular weight distribution (Mw / Mn) of the oxyalkylene polymer having a crosslinkable silicon group is preferably 2 or less, particularly preferably 1.6 or less.

  Examples of the synthesis method of the polyoxyalkylene polymer include, but are not particularly limited to, a polymerization method using an alkali catalyst such as KOH, a polymerization method using a double metal cyanide complex catalyst, and the like. According to the polymerization method using a double metal cyanide complex catalyst, a polyoxyalkylene polymer having a number average molecular weight of 6,000 or more and a high molecular weight of Mw / Mn of 1.6 or less and a narrow molecular weight distribution can be obtained.

  The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component. Examples of the urethane bond component are obtained from a reaction between an aromatic polyisocyanate such as toluene (tolylene) diisocyanate and diphenylmethane diisocyanate; an aliphatic polyisocyanate such as isophorone diisocyanate and a polyoxyalkylene polymer having a hydroxyl group. Ingredients can be mentioned.

  A polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group, or an isocyanate group in the molecule is reacted with a functional group having reactivity with the functional group and a crosslinkable silicon group. Can introduce a crosslinkable silicon group into a polyoxyalkylene polymer (hereinafter referred to as a polymer reaction method).

  As an example of a polymer reaction method, hydrosilylation or mercaptosis is caused by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer. The method of obtaining the polyoxyalkylene type polymer which has can be mentioned. An unsaturated group-containing polyoxyalkylene-based polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group. A polyoxyalkylene polymer containing can be obtained.

  Other examples of the polymer reaction method include a method in which a polyoxyalkylene polymer having a hydroxyl group at the terminal is reacted with an isocyanate group and a crosslinkable silicon group, or a polyoxyalkylene polymer having an isocyanate group at the terminal. Examples thereof include a method of reacting an union with an active hydrogen group such as a hydroxyl group or an amino group, and a crosslinkable silicon group. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.

  The polyoxyalkylene polymer having a crosslinkable silicon group may be used alone or in combination of two or more.

  Various monomers can be used as the (meth) acrylic acid ester monomer constituting the main chain of the (meth) acrylic acid ester polymer. For example, (meth) acrylic acid monomers such as acrylic acid; (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid n-butyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic (Meth) acrylic acid alkyl ester monomers such as stearyl acid; alicyclic (meth) acrylic acid ester monomers; aromatic (meth) acrylic acid ester monomers; (meth) acrylic acid 2-methoxyethyl (meta) ) Acrylic ester monomers; silyl group-containing (meth) acrylic ester monomers such as γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane; (meth) acrylic acid derivatives; Fluorine-containing (meth) acrylic acid ester monomers It is.

  In the (meth) acrylic acid ester polymer, the following vinyl monomers can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of vinyl monomers include styrene, maleic anhydride, vinyl acetate and the like. In addition to these, acrylic acid and glycidyl acrylate may be contained as monomer units (hereinafter also referred to as other monomer units).

  These may be used alone or may be copolymerized. From the viewpoint of physical properties of the product, a polymer composed of a (meth) acrylic acid monomer is preferable. Moreover, the (meth) acrylic acid ester type polymer which used the 1 type (s) or 2 or more types (meth) acrylic-acid alkylester monomer and used together with the other (meth) acrylic acid monomer as needed is more preferable. Furthermore, the number of silicon groups in the (meth) acrylic acid ester polymer can be controlled by using the silyl group-containing (meth) acrylic acid ester monomer in combination. A methacrylic acid ester polymer comprising a methacrylic acid ester monomer is particularly preferred because of its good adhesion. In addition, when the viscosity is reduced, the flexibility is imparted, and the tackiness is imparted, an acrylate monomer is preferably used as appropriate. In the present embodiment, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  As a method for producing the (meth) acrylic acid ester polymer, for example, a radical polymerization method using a radical polymerization reaction can be used. The radical polymerization method includes a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, or a controlled radical capable of introducing a reactive silyl group at a controlled position such as a terminal. A polymerization method is mentioned. However, a polymer obtained by a free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator generally has a large molecular weight distribution value of 2 or more and a high viscosity. Therefore, when obtaining a (meth) acrylate polymer having a narrow molecular weight distribution and low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high rate, It is preferable to use a controlled radical polymerization method.

  Examples of the controlled radical polymerization method include a free radical polymerization method and a living radical polymerization method using a chain transfer agent having a specific functional group. Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization method, radical polymerization method using transition metal complex (Transition-Metal-Mediated Living Radical Polymerization), atom transfer radical polymerization method (Atom-Transfer-Radical-Polymerization; ATRP), etc. It is preferable to employ a living radical polymerization method such as Further, a reaction using a thiol compound having a reactive silyl group and a reaction using a thiol compound having a reactive silyl group and a metallocene compound are also preferable.

  These organic polymers having a crosslinkable silicon group may be used alone or in combination of two or more. Specifically, a group consisting of a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth) acrylic acid ester polymer having a crosslinkable silicon group. An organic polymer obtained by blending two or more selected from the above can also be used. In particular, an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group has excellent characteristics. When applied to the sealing material composition according to the present embodiment, the elongation rate at the maximum load and the adhesive force can be increased.

There are various methods for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group. For example, it has a crosslinkable silicon group and the molecular chain is substantially the general formula (3):
_{^{-CH 2 -C (R 3) (}} COOR 4) - ··· (3)
(Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group having 1 to 5 carbon atoms) and a general formula (4):
—CH ₂ —C (R ³ ) (COOR ⁵ ) — (4)
(Wherein R ³ is the same as described above, and R ⁵ represents an alkyl group having 6 or more carbon atoms) A copolymer composed of a (meth) acrylic acid ester monomer unit is represented by a crosslinkable silicon group And a method of blending and producing a polyoxyalkylene-based polymer having.

As R ^{4 in the} general formula (3), for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group and the like have 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, Preferably, an alkyl group having 1 to 2 carbon atoms is used. The alkyl group of R ⁴ may alone, or may be a mixture of two or more.

R ^{5 in the} general formula (4) is, for example, a long group having 6 or more carbon atoms such as 2-ethylhexyl group, lauryl group, stearyl group, etc., usually 7 to 30 carbon atoms, preferably 8 to 20 carbon atoms. Chain alkyl groups. The alkyl group of R ⁵ is as in the case of R ^4, may be alone or in admixture.

  The molecular chain of the (meth) acrylic ester copolymer is substantially composed of monomer units of the formulas (3) and (4). Here, “substantially” means that the total of the monomer units of the formula (3) and the formula (4) present in the copolymer exceeds 50% by mass. The total of the monomer units of the formula (3) and the formula (4) is preferably 70% by mass or more. The abundance ratio of the monomer unit of the formula (3) and the monomer unit of the formula (4) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40, by mass ratio.

  (Meth) having a crosslinkable silicon group used in a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group with a (meth) acrylic acid ester polymer having a crosslinkable silicon group As the acrylic ester polymer, for example, a (meth) acrylic acid alkyl ester monomer unit having a crosslinkable silicon group and having a molecular chain substantially having (1) an alkyl group having 1 to 8 carbon atoms; (2) (meth) acrylic acid ester-based copolymers such as (meth) acrylic acid ester-based copolymers containing (meth) acrylic acid alkyl ester monomer units having an alkyl group having 10 or more carbon atoms Coalescence can also be used.

  The number average molecular weight of the (meth) acrylate polymer is such that when the glass transition temperature (Tg) of the (meth) acrylate polymer is less than 0 ° C., for example, the (meth) acrylate polymer is acrylic. When mainly composed of acid butyl monomer units, 20,000 or more is preferable, 30,000 or more is more preferable, 35,000 or more is further preferable, and 40,000 or more is particularly preferable. Further, when the glass transition temperature (Tg) of the (meth) acrylate polymer is 0 ° C. or higher, for example, when the (meth) acrylate polymer is mainly composed of methyl methacrylate monomer units, The number average molecular weight is preferably from 600 to 10,000, more preferably from 600 to 5,000, still more preferably from 1,000 to 4,500. By setting the number average molecular weight within this range, compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group is improved. The (meth) acrylic acid ester polymer may be used alone or in combination of two or more. There is no particular limitation on the mixing ratio of the polyoxyalkylene polymer having a crosslinkable silicon group and the (meth) acrylic acid ester polymer having a crosslinkable silicon group, but the (meth) acrylic acid ester polymer When the glass transition temperature (Tg) is less than 0 ° C., for example, when the (meth) acrylate polymer is mainly composed of butyl acrylate monomer units, the (meth) acrylate polymer and polyoxy It is preferable that the (meth) acrylic acid ester polymer is within a range of 30 parts by mass or more and 90 parts by mass or less, and 40 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass in total with the alkylene polymer. More preferably, it is in the range, and more preferably in the range of 50 parts by mass or more and 70 parts by mass or less. When the amount of the (meth) acrylic acid ester polymer is more than 90 parts by mass, the viscosity becomes high and workability deteriorates, which is not preferable. Further, when the glass transition temperature (Tg) of the (meth) acrylate polymer is 0 ° C. or higher, for example, when the (meth) acrylate polymer is mainly composed of methyl methacrylate monomer units, The (meth) acrylic acid ester polymer is within the range of 10 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass in total of the (meth) acrylic acid ester polymer and the polyoxyalkylene polymer. Is preferable, the range of 20 parts by mass or more and 50 parts by mass or less is more preferable, and the range of 25 parts by mass or more and 45 parts by mass or less is more preferable. When the amount of the (meth) acrylic acid ester-based polymer is more than 60 parts by mass, the viscosity is increased, and workability is deteriorated.

  Furthermore, in this embodiment, an organic polymer obtained by blending a saturated hydrocarbon polymer having a crosslinkable silicon group and a (meth) acrylic acid ester copolymer having a crosslinkable silicon group can also be used. As another method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a crosslinkable silicon group, in the presence of an organic polymer having a crosslinkable silicon group (meta ) A method of polymerizing an acrylate monomer can be used.

(B component: monofunctional epoxy compound)
As the compound (B) component which has one epoxy group and does not have a crosslinkable silicon group (hereinafter also referred to as monofunctional epoxy compound) according to the present embodiment, alkyl monoglycidyl ether, phenyl Glycidyl ether, linear alcohol monoglycidyl ether, polyglycol glycidyl ether, glycidyl ether such as glycidyl methacrylate, glycidyl ester or a mixture thereof, 1,2 epoxy dodecane, epoxy hydrocarbon such as styrene oxide or a mixture thereof, cyclohexane oxide, 4-vinylepoxycyclohexane, 3,4-epoxycyclohexylmethanol, 3,4-epoxycyclohexylmethyl methacrylate, epoxyhexahydrophthalic acid di-2-ethylhexyl, epoxy hex Hydrophthalic di-2-ethylhexyl, alicyclic epoxy compounds represented by the following formula (a) ~ (g), and the like. In these, an alicyclic epoxy compound is preferable.

  (B) The usage-amount of a monofunctional epoxy compound is the range of 1-100 mass parts with respect to 100 mass parts of organic polymers which have a crosslinkable silicon group of (A) component.

Here, by adding a compound having one epoxy group in the molecule and not having a crosslinkable silicon group, the flexibility of the cured product can be improved, and the elongation characteristics can be lowered after being immersed in water or exposed to heat. Can be prevented. The sealant composition according to the present embodiment can have an initial 50% tensile modulus at a test temperature of 23 ° C. measured in accordance with a siding sealant standard of less than 0.2 N / mm ² . The component (B) is required not to have a crosslinkable silicon group. In the case of having a crosslinkable silicon group, the crosslinkable silicon group causes a crosslinking reaction with the polymer of the component (A), so that it may be difficult to improve flexibility.

(C component: ketiminated aminosilane compound)
The sealing material composition according to this embodiment reacts with water as component (C) to produce an amine compound having at least one alkoxysilyl group in one molecule (ketiminated aminosilane compound). May be contained. The alkoxysilyl group is a silicon atom-containing group in which an alkoxy group is bonded to a silicon atom. Examples of such a compound include a compound obtained by ketiminizing an amino group of an amine compound having an alkoxysilyl group (hereinafter also referred to as an aminosilane compound) with a carbonyl compound. Examples of aminosilane compounds that undergo ketimination include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2aminoethyl) aminopropyltrimethoxysilane, and γ- (2aminoethyl) aminopropyltriethoxy. Examples thereof include silane and γ- (2aminoethyl) aminopropylmethyldimethoxysilane.

  Moreover, as a carbonyl compound, the carbonyl compound demonstrated in the column of the ketimine compound which does not have a crosslinkable silicon group mentioned later can be used. When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like.

  When the component (C) such as a compound having an amino group ketiminized is used, it does not react with the epoxy resin during storage of the composition, so that a one-component composition can be obtained. The component (C) acts as an adhesiveness imparting agent, and also acts as an epoxy resin curing agent and curing catalyst. (C) A component can also be used in combination of 2 or more types.

  The amount of component (C) used can be added in the range of 0.1 to 20 parts by mass, preferably in the range of 1 to 10 parts by mass, per 100 parts by mass of the polymer of component (A).

(Other compounding substances)
The sealing material composition according to this embodiment includes a polyfunctional epoxy resin, a ketimine compound having no crosslinkable silicon group, an epoxy resin curing agent other than the component (C), a plasticizer, a filler, a silanol condensation catalyst, and a silane coupling. Agents, diluents, dehydrating agents, anti-aging agents, ultraviolet absorbers, lubricants, pigments, foaming agents and the like may be further added.

  The sealing material composition according to the present embodiment may contain a polyfunctional epoxy resin as long as the effect of the sealing material according to the present embodiment is not impaired. As the polyfunctional epoxy resin, various epoxy resins which are compounds having two or more epoxy groups in the molecule can be used. Examples of the epoxy resin include an epichlorohydrin-bisphenol A type epoxy resin, an epichlorohydrin-bisphenol F type epoxy resin, a flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, a novolac type epoxy resin, and a hydrogenated bisphenol A type epoxy resin. , Glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N, N diglycidyl aniline, N, N diglycidyl-o toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, Glycidyl ethers of polyhydric alcohols such as glycerin, hydantoin type epoxy resins, epoxidized products such unsaturated polymers such as petroleum resins. Among these epoxy resins, a compound containing at least two epoxy groups represented by the following formula (5) in the molecule has high reactivity during curing, and the cured product forms a three-dimensional network. It is preferable from the viewpoint of ease.

  Further, as the polyfunctional epoxy resin, epoxy resins having an aromatic ring such as bisphenol A type epoxy resins, or bisphenol F type epoxy resins, bisphenol AD type epoxy resins, and novolac type epoxy resins are more preferable. Among such epoxy resins having an aromatic ring, from the viewpoint of adhesion to a substrate, the epoxy resin has an aromatic ring and does not have an oxyalkylene chain which is a segment imparting flexibility. Is particularly preferred. Furthermore, bisphenol A type epoxy resins are most preferable, and bisphenol A type epoxy resins having no oxyalkylene chain are particularly preferable. A compound having two or more epoxy groups in the molecule has a function of improving the adhesiveness of an organic polymer having a crosslinkable silicon group, particularly an oxyalkylene polymer having a crosslinkable silicon group. The epoxy resin is preferably liquid at normal temperature. Moreover, it is preferable that the molecular weight of an epoxy resin is 500 or less.

  The usage-amount of a polyfunctional epoxy resin is the range of 1-50 mass parts with respect to 100 mass parts of (A) organic polymers which have a crosslinkable silicon group. When it is less than 1 part by mass, the adhesiveness of the cured product of the sealing material composition becomes insufficient, and when it exceeds 50 parts by mass, the flexibility of the cured product of the sealing material composition becomes insufficient. A preferable range is 1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, and further preferably 1 part by mass or more and 10 parts by mass or less.

  The sealing material composition according to this embodiment has a ketimine group in the molecule and does not have a crosslinkable silicon group (hereinafter also referred to as ketimine) as long as the effect of the sealing material according to this embodiment is not impaired. That is, you may contain the ketimine compound which does not have a crosslinkable silicon group. By adding a ketimine compound having no crosslinkable silicon group to the sealing material composition, the rate of change in the modulus of the cured product of the sealing material composition can be lowered. That is, by adding a ketimine compound having no crosslinkable silicon group to the sealing material composition, it is possible to suppress the modulus from exceeding a predetermined value even after the cured product of the sealing material composition is exposed to heat, While maintaining flexibility, it is possible to suppress a decrease in elongation at break after immersion in water or exposure to heat.

  Ketimine is stably present in the absence of moisture and is decomposed into primary amines and ketones by moisture, and the resulting primary amine acts as a silanol condensation catalyst. Thereafter, by reacting with the epoxy resin, the silanol condensation catalytic action expires, and the cured product can be maintained at a low modulus even after being exposed to heat. In addition, when ketimine is used, it does not react with the epoxy resin during the storage of the composition, so that a one-component composition can be obtained. Such ketimines can be obtained by a condensation reaction between an amine compound and a carbonyl compound.

  Various amine compounds and carbonyl compounds can be used for the synthesis of ketimine. Examples of amine compounds include monoamines such as 2-ethylhexylamine, laurylamine, stearylamine, i-stearylamine; diamines such as ethylenediamine, tetramethylenediamine, and hexamethylenediamine; 1,2,3-triaminopropane, tetra Polyamines such as (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine and triethylenetriamine; polyoxyalkylene polyamines and the like can be used.

  Examples of the carbonyl compound include aldehydes such as acetaldehyde and benzaldehyde; cyclic ketones such as cyclohexanone; aliphatic ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; β-dicarbonyl such as acetylacetone, ethyl acetoacetate, and diethyl malonate. A compound or the like can be used. When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like.

  For the purpose of keeping the cured product of the sealing material flexible, it is possible to use a ketiminated monoamine obtained by a condensation reaction of a monoamine and a carbonyl compound or a ketiminated diamine obtained by a condensation reaction of a diamine and a carbonyl compound. Preferably, a ketiminated monoamine is used. These ketimines may be used alone or in combination of two or more. Moreover, the usage-amount of the ketimine compound which does not have a crosslinkable silicon group can be used in the range of 0.1-20 mass parts with respect to 100 mass parts of polymers of (A) component, 1-10 mass parts can be used. It is preferable to use within a range.

As the epoxy resin curing agent other than the component (C), one or a plurality of various epoxy resin curing agents can be selected and used. Examples of such epoxy resin curing agents include amines, acid anhydrides, imidazoles, and other curing agents. However, a highly active curing agent may be difficult to cure the epoxy resin at room temperature to form a one-component composition, so it should be used within the range in which the purpose of the sealing material according to this embodiment is achieved. preferable.

  Examples of plasticizers include phthalates such as dioctyl phthalate; aliphatic dibasic esters such as dioctyl adipate; glycol esters; aliphatic esters; phosphate esters; polyester plasticizers; Examples thereof include polyethers such as derivatives thereof; hydrocarbon plasticizers; chlorinated paraffins; low molecular weight acrylic ester polymers and the like. These plasticizers may be used alone or in combination of two or more.

  When using a plasticizer, 10-300 mass parts can be used with respect to 100 mass parts of (A) component, and it is preferable to use in the range of 20-250 mass parts. When the amount of the plasticizer used is less than 10 parts by mass, the viscosity of the composition may become too high. When the amount used exceeds 300 parts by mass, the plasticizer oozes out of the cured product. Since there are cases, it is not preferable. The sealing material composition according to the present embodiment produces a non-plastic blending sealing material composition that does not contain a low molecular weight plasticizer having a molecular weight of 800 or less and further a molecular weight of 1000 or less, such as a phthalate ester plasticizer. It is particularly useful in cases.

  Fillers include reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, hardened titanium, bentonite, organic bentonite Further, fillers such as ferric oxide, zinc oxide, activated zinc white, and shirasu balloon; fibrous fillers such as asbestos, glass fibers, and filaments can be used.

  When producing a cured product having high strength by adding these fillers, it is preferable to use a filler selected mainly from fumed silica, carbon black, surface-treated fine calcium carbonate, and the like. In the case of producing a cured product having low strength and high elongation, it is preferable to use a filler selected mainly from titanium oxide, calcium carbonate, magnesium carbonate, shirasu balloon, and the like. These fillers may be used alone or in combination of two or more.

  When using a filler, it can be used in the range of 1 to 300 parts by weight, preferably in the range of 5 to 300 parts by weight, and in the range of 5 to 250 parts by weight with respect to 100 parts by weight of the component (A). More preferably, it is used.

  Examples of the silanol condensation catalyst include dibutyltin dilaurate, dibutyltin diacetate, a reaction product of dioctyltin oxide and a silicate compound, an organic tin compound such as a reaction product of dibutyltin oxide and a phthalate ester: tin carboxylate, carboxyl Carboxylic acid metal salts such as bismuth acid and iron carboxylate: aliphatic amines, aromatic amines, amidines such as DBU, guanidines such as diphenylguanidine, amine compounds such as biguanides: carboxylic acids such as versatic acid: Titanium compounds such as diisopropoxy titanium bis (ethyl acetocetate), alkoxy metals such as aluminum compounds: inorganic acids: boron trifluoride complexes such as boron trifluoride ethylamine complex: aluminum monoacetylacetonate bis (ethyl acetoacetate ) Etc. metal Rate compounds. Of these, organotin compounds are preferred. The silanol condensation catalyst acts as a curing catalyst for the polymer having a crosslinkable silicon group as the component (A). When using a silanol condensation catalyst, it can be used in the range of 0.1 to 20 parts by mass, preferably in the range of 0.2 to 10 parts by mass, with respect to 100 parts by mass of the component (A).

  The sealing material composition according to the present embodiment can further contain a silane coupling agent. The sealing material composition according to the present embodiment can improve adhesion to general adherends such as metal, plastic, and glass by blending a silane coupling agent.

  Examples of silane coupling agents include mercapto group-containing silanes; vinyl unsaturated group-containing silanes; chlorine atom-containing silanes; isocyanate-containing silanes; alkyl silanes; phenyl group-containing silanes; isocyanurate group-containing silanes. However, it is not limited to these. Also, modified amino group-containing silanes in which amino groups are modified by reacting amino group-containing silanes with epoxy group-containing compounds, isocyanate group-containing compounds, and (meth) acryloyl group-containing compounds containing the above silanes are used. May be.

  The blending ratio of the silane coupling agent is, for example, preferably 0.2 to 20 parts by mass, more preferably 0.3 to 15 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing polymer. More preferably, it is 5-10 mass parts. These silane coupling agents may be used alone or in combination of two or more.

  The sealing material composition according to the present embodiment preferably further contains a diluent. By containing a diluent, physical properties such as viscosity can be adjusted. Various diluents can be used as the diluent. Diluents include, for example, saturated hydrocarbon solvents such as normal paraffin and isoparaffin, α-olefin derivatives such as linearlen dimer (trade name of Idemitsu Kosan Co., Ltd.), aromatic hydrocarbon solvents, alcohol solvents, and ester solvents. Examples of the solvent include various solvents such as a solvent, a citrate ester solvent such as acetyltriethyl citrate, and a ketone solvent.

  When considering the safety of the obtained sealant composition, it is desirable that the flashpoint of the sealant composition is high, and it is preferable that the volatile substances from the sealant composition are small. Therefore, the flash point of the diluent is preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. When mixing 2 or more types of diluents, it is preferable that the flash point of the mixed diluent is 70 degreeC or more. However, since a diluent generally having a high flash point tends to have a low dilution effect on the sealant composition, it is preferable to use a diluent having a flash point of 250 ° C. or lower.

  When considering both the safety and the dilution effect of the sealing material composition according to the present embodiment, the diluent is preferably a saturated hydrocarbon solvent, more preferably normal paraffin or isoparaffin. The normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms.

  It is preferable to mix | blend the mixture ratio of a diluent in the range of 0-50 mass parts with respect to 100 mass parts of (A) organic polymers, and it is more preferable to mix | blend in the range of 0.1-30 mass parts. More preferably, it is blended in the range of 0.1 to 15 parts by mass. The diluent can be used alone or in combination of two or more.

  Examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, tetraethoxysilane, and tetramethoxysilane; ester compounds such as methyl orthoformate and ethyl orthoformate. These dehydrating agents can be used alone or in combination of two or more. As the dehydrating agent, vinyltrimethoxysilane is particularly preferable.

  It is preferable to mix | blend content of a dehydrating agent in 0.5-20 weight part with respect to 100 mass parts of (A) component, and it is more preferable to mix | blend in 1-15 weight part. If the content of the dehydrating agent in the sealing material composition is too low, the effect obtained by the dehydrating agent may not be sufficient. Moreover, when content of the dehydrating agent in a sealing material composition is too high, the sclerosis | hardenability of a sealing material composition may fall.

(Primer layer 30)
The primer layer 30 can be provided on the side surface of the first adherend 10 and the side surface of the second adherend 20. Specifically, the primer layer 30 includes at least one reactive resin selected from the group consisting of a synthetic rubber resin, an acrylic resin, a urethane resin, an epoxy resin, a silicone resin, and a silane resin, and silane. It is formed by applying a primer containing a coupling agent and an organic solvent to the side surface of the first adherend 10 and the side surface of the second adherend 20.

(Backup material 40)
The backup material 40 is formed of an elastic material, and can be formed using natural rubber, a synthetic resin such as styrene / butadiene / styrene block copolymer (SBS), and / or a foam thereof. The backup material 40 has an adhesive layer or an adhesive layer that can be attached to the bottom of the gap along the gap between the first adherend 10 and the second adherend 12. Configured.

  Since the cured product of the sealing material composition according to the present embodiment is excellent in flexibility after heating (low modulus), it can be used as a sealing material, particularly as a sealing material for siding boards such as buildings. Further, the cured product of the sealing material composition according to the present embodiment can be used for frame members such as window frames and door frames, seals at the boundary between eaves and the like and wall materials, and the like.

[About joint construction method]
The wall having the joint structure according to the present embodiment is manufactured along the following steps. First, a gap between the first adherend 10 and the second adherend 12 disposed at an adjacent position with a gap between the first adherend 10 and each adherend. The area where the body sealing material comes into contact is cleaned (cleaning process). Next, the backup material 40 is placed in a gap between the first adherend 10 and the second adherend 12 disposed at an adjacent position with a gap between the first adherend 10. Is loaded (backup material loading step). Then, a masking tape is applied to the edge of the joint, that is, the gap-side edge of the first adherend 10 and the gap-side edge of the second adherend 12 (mask process).

  Subsequently, a primer is applied to the surface facing the gap of the first adherend 10 and the surface facing the gap of the second adherend 12 as necessary (primer application step). Then, the gap on the backup material 40 is filled with a one-component room temperature moisture-curing sealing material composition having a low modulus change rate after heating (filling step). Next, the surface of the one-component room temperature moisture-curing sealant composition is finished smoothly (a spatula finishing step). After the spatula finishing process, the masking tape is removed (mask removing process). Then, curing is performed for a predetermined time (curing process). Thereby, the wall which has the joint structure concerning this embodiment is produced.

(Effect of embodiment)
The wall having the joint structure according to the present embodiment has a modulus at the time of 50% elongation after heating and a modulus at the time of 50% elongation after heating in the gap between the first adherend 10 and the second adherend 12. Since the rate of change in modulus, the rate of elongation at the maximum load after heating, and the rate of change in the rate of elongation at the maximum load after heating are filled with a sealing material 20 in a predetermined range, flexibility, elongation characteristics In addition, since the adhesiveness is less likely to deteriorate with time in a natural environment, it is possible to extend the life of a building such as a house.

  Further, the sealing material 20 according to the present embodiment is formed from a one-component room temperature moisture-curing sealing material composition, and the one-component room temperature moisture-curing sealing material, which is a cured product of the one-component room temperature moisture-curing sealing material composition, The decrease in elongation characteristics due to heat exposure is small. Therefore, the sealing material 20 according to the present embodiment can suppress a decrease in elongation characteristics over time.

  Further, the sealing material according to the present embodiment has a low modulus change rate after heating, and can maintain high flexibility for a long period of time. Therefore, the sealing material according to the present embodiment can be used for applications that are exposed to the outdoors for a long period of time, or can be used around the water in a bathroom or kitchen even indoors. In particular, it can be suitably applied to a sealing material for siding boards that is used outdoors and requires water resistance against heat resistance and rainwater. In addition, the sealing material according to the present embodiment is preferably used as a sealing material for ceramics siding boards, which is a porous material that easily absorbs moisture, because the decrease in adhesion due to moisture entering the ceramics siding board is small. Can do.

  Hereinafter, the wall having the joint structure according to the present embodiment will be described in detail using examples.

(Synthesis Example 1: Crosslinkable silicon group-containing organic polymer (A1 component) having a number average molecular weight of 15,000 or more)
62.7% by weight of butyl acrylate, 18.3% by weight of ethyl acrylate, 19.0% by weight of stearyl acrylate, diethyl 2,5-dibromoadipate and ethyl α-bromobutyrate as initiator, and bromide as polymerization catalyst Atom transfer radical polymerization method (ATRP) using monocopper and pentamethyldiethylenetriamine, 1,7-octadiene as dienating agent, methyldimethoxysilane as silylating agent, and according to the method of Production Example 1 of JP 2010-11644 A A polyacryl skeleton organic polymer having a polystyrene-equivalent number average molecular weight of 45,000, having methyldimethoxysilyl groups at both ends and having 1.8 crosslinkable silicon groups in one molecule on average. (A1 component) was obtained.

(Synthesis Example 2: Crosslinkable silicon group-containing organic polymer (A2 component) having a number average molecular weight of 15,000 or more)
Propylene glycol was used as an initiator, and propylene oxide was reacted in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to obtain a hydroxyl-terminated polyoxypropylene having a number average molecular weight of 29,000. A methanol solution of NaOCH ₃ was added to the hydroxyl group-terminated polyoxypropylene polymer to distill off the methanol, and allyl chloride was further added to convert the hydroxyl group at the end to an allyl group. After the desalting and purification treatment, methyldimethoxysilane, which is a hydrosilyl compound, is reacted in the presence of a platinum catalyst to have a methyldimethoxysilyl group at the end, and an average of 1.8 crosslinkable silicon groups per molecule. A polyoxypropylene skeleton organic polymer (A2 component) having a number average molecular weight of 29,000 was obtained. The number average molecular weight is a polystyrene-equivalent molecular weight measured by gel permeation chromatography using Tosoh's HLC-8120GPC as the liquid delivery system, the column using Tosoh's TSK-GELH type, and the solvent using THF.

(Synthesis Example 3: Crosslinkable silicon group-containing organic polymer A′1 having a number average molecular weight of 15,000 or more)
68% by weight of butyl acrylate, 10% by weight of methyl methacrylate, 20% by weight of stearyl methacrylate, 2% by weight of 3-methacryloxypropylmethyldimethoxysilane, isobutanol as a solvent for polymerization, V-59 as a polymerization initiator Using a drug (manufactured by Yakuhin Co., Ltd.) and reacting by a method according to the method of Synthesis Example 3 of JP 2010-95704 A, with an isobutanol solution having a solid concentration of 60%, methyldimethoxysilyl groups are placed at random positions. Thus, an organic polymer (A′1 component) having a polyacryl skeleton having a number average molecular weight of 20,000 in terms of polystyrene having two crosslinkable silicon groups in one molecule on average was obtained. Next, an isobutanol solution of the polyacrylic skeleton polymer (1) obtained above to the polyoxypropylene skeleton organic polymer (component A2) obtained in Synthesis Example 2 is used in a solid content ratio (weight ratio). Was mixed at a ratio of 70/30, and isobutanol was removed under reduced pressure by heating. As a result, an organic polymer A′1 according to Synthesis Example 3 was obtained. In Example 5 of Table 1, the solid weights of the polymer (1) and the organic polymer (component A2) are shown separately (that is, the organic polymer A′1 is 70 The organic polymer (A2 component) and 30 parts by mass of the polymer (1) are included.

(Examples 1-5, Comparative Example 1)
A one-component sealant composition having the composition shown in Table 1 was prepared, and a test sample using the sealant composition was prepared. Using this test sample, the initial properties and the tensile properties after heating exposure (heating) (modulus at 50% elongation, elongation at maximum load) were measured. The results are shown in Table 1. The preparation of the composition and test sample and the test method are as follows.

  The organic polymer (component A1) obtained in Synthesis Example 1 and Synthesis Example 2 as an oxyalkylene polymer having a crosslinkable silicon group (A) and a number average molecular weight of 15,000 or more shown in Table 1, and organic A polymer (component A2) or organic polymer A′1, a filler, a plasticizer, a dehydrating agent, a silanol condensation catalyst, and a diluent are blended in the parts by mass shown in Table 1, and heating and vacuum mixing and stirring are performed at 110 ° C. The mixture was dehydrated for 2 hours. Furthermore, a predetermined amount of the monofunctional epoxy compound of component (B) (excluding Comparative Example 1) and the alkoxysilane compound of component (C) were added and stirred to prepare a sealing material composition.

In Table 1, the compounding quantity of each compounding substance is shown in parts by mass. Details of each compounding substance are as follows.
* 1 Epoxyhexahydrophthalate di-2-ethylhexyl (Shinsocizer E-PS, manufactured by Shin Nippon Rika Co., Ltd.)
* 2 Compound obtained by ketiminizing γ-aminopropyltrimethoxysilane with MIBK * 3 Fatty acid-treated heavy calcium carbonate (manufactured by Maruo Calcium Co., Ltd., MC coat S-1)
* 4 Fatty acid-treated colloidal calcium carbonate (Maruo Calcium Co., Ltd., Calfine 500)
* 5 Non-functional acrylic polymer, weight average molecular weight 2500 (manufactured by Toagosei Co., Ltd., ARUFON UP-1110)
* 6 Vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM1003)
* 7 Dibutyltin diacetylacetonate (manufactured by Nitto Kasei Co., Ltd., Neneostan U-220H)
* 8 Normal paraffin [main component, n-undecane] (manufactured by Japan Energy, Cactus normal paraffin N-11)

(Creation of test sample)
In accordance with the siding sealant standard, an I-shaped test body described in 5.1.6 of the same standard was produced. That is, the ceramic plate was cut into a size of 50 mm in length and 50 mm in width, and two cut ceramic plates were fixed so that the vertical direction was opposed at an interval of 10 mm. A foamed polyethylene backup material having a length of 50 mm, a width of 10 mm, and a thickness of 6 mm was placed on the lower surface of the gap, and the surface of the ceramic plate was covered with a masking tape. Then, a primer (MP-1000 manufactured by Cemedine Co., Ltd.) is applied to a region that comes into contact with the sealing material, and after filling the sealing material into a gap (joint) with a space of 10 mm to a thickness of 8 mm, the masking tape is removed, After curing in a 23 ° C. 50% RH environment for 28 days to cure the sealing material, the backup material was removed and a test sample was prepared.

(Heat exposure (heating) test)
The test sample was heated in an oven at 80 ° C. for 14 days, cooled to room temperature, and then measured for tensile properties.

(Tensile adhesion measurement method)
A tensile adhesion test was performed in accordance with the siding sealant standard (test temperature 23 ° C.). After curing, a tensile adhesion test was conducted at a tensile speed of 50 mm / min in a 23 ° C. environment. Then, the load when the elongation was 50%, the maximum load, and the amount of elongation at the maximum load were measured. Furthermore, the measurement results were evaluated based on the following criteria.

(After heating)
As for the modulus, the modulus at 50% elongation and the rate of change [| (modulus at 50% elongation after heating) − (modulus at initial 50% elongation) | / (modulus at initial 50% elongation) × 100], when the modulus is 0.13 N / mm ² or less and the rate of change is 20% or less, “◎”, and when the modulus is 0.15 N / mm ² or less, the rate of change is 30% or less (however, the modulus is 0.00). “○” in the case of 13 N / mm ² or less and excluding the change rate of 20% or less), the modulus is 0.2 N / mm ² or less and the change rate is 40% or less (however, the modulus is 0.15 N / mm ² or less) When the rate of change was 30% or less, “Δ”, and when the modulus exceeded 0.2 N / mm ² and the rate of change exceeded 40%, “X” was evaluated.

  For the elongation rate at the maximum load, the elongation rate at the maximum load and its change rate [| (elongation rate at the maximum load after heating) − (elongation rate at the initial maximum load) | / (initial maximum load) When the elongation rate is 500% or more and the change rate is 20% or less, “◎”, when the elongation rate is 400% or more and the change rate is 30% or less (however, the elongation rate) Is ≧ 500% and the rate of change is 20% or less) “○”, the rate of extension is 300% or more and the rate of change is 40% or less Excluding) “△”, when the elongation rate was less than 300% and the rate of change exceeded 40%, it was evaluated as “x”.

As shown in Table 1, in Examples 1 to 5, the modulus after heating is as small as 0.15 N / mm ² or less, the rate of change is 25% or less, and the elongation at the maximum load is about 560. It was shown that the rate of change was 5% or less when the content was greater than or equal to 5%.

  While the embodiments and examples of the present invention have been described above, the embodiments and examples described above do not limit the invention according to the claims. In addition, not all the combinations of features described in the embodiments and examples are essential to the means for solving the problems of the invention, and various combinations are possible without departing from the technical idea of the present invention. It should be noted that variations are possible.

DESCRIPTION OF SYMBOLS 1 Wall which has joint structure 10 1st to-be-adhered body 12 2nd to-be-adhered body 20 Sealing material 30 Primer layer 40 Backup material

Claims (5)

A wall having a joint structure of a structure,
A first adherend;
A second adherend disposed at a position adjacent to the first adherend with a gap between;
In the results of the tensile adhesion test in which the gap is filled through a primer and tested according to JTC S-0001 ceramics siding sealant JTC standard,
The modulus at 50% elongation after heating at 80 ° C. for 14 days is less than 0.15 N / mm ² ,
The rate of change in modulus at 50% elongation after heating at 80 ° C. for 14 days is 40% or less,
The elongation rate at the maximum load after heating at 80 ° C. for 14 days is 300% or more,
A wall having a joint structure comprising : a one-component room temperature moisture-curing sealing material having a rate of change in elongation at maximum load after heating at 80 ° C. for 14 days of 40% or less .   The wall having a joint structure according to claim 1, wherein the first adherend and the second adherend are siding materials. A wall having a joint structure of a structure,
A first adherend;
A second adherend disposed at a position adjacent to the first adherend with a gap between;
A one-component room temperature moisture-curing sealing material filled in the gap via a primer, wherein the one-component room temperature moisture-curing sealing material is,
(A1 component) a polymer whose main chain skeleton is composed of butyl acrylate monomer units having a number average molecular weight of 20,000 or more;
(A2 component) a polymer having a main chain skeleton of an oxyalkylene polymer and having a crosslinkable silicon group at the end;
(B) a monofunctional epoxy compound;
(C) an alkoxysilane compound that reacts with water to produce an amine compound having at least one alkoxysilyl group in one molecule ;
A one-component room temperature moisture-curing sealing material composition in which the (A1 component) is within a range of 30 parts by mass or more and 90 parts by mass or less with respect to a total of 100 parts by mass of the (A1 component) and the (A2 component). wall with is that the eye area structure obtained by curing. The wall having a joint structure according to claim 3, wherein (A1 component) is a polymer obtained by reacting at least butyl acrylate with diethyl 2,5-dibromoadipate. A backup material for loading a backup material into the gap between the first adherend and the second adherend disposed at an adjacent position with a gap between the first adherend and the first adherend. Loading process;
A primer application step of applying a primer to the surface of the first adherend facing the gap and the surface of the second adherend facing the gap;
In the tensile adhesion test results tested according to JTC S-0001 ceramics siding sealant JTC standard after curing the gap on the backup material ,
The modulus at 50% elongation after heating at 80 ° C. for 14 days is less than 0.15 N / mm ² ,
The rate of change in modulus at 50% elongation after heating at 80 ° C. for 14 days is 40% or less,
The elongation rate at the maximum load after heating at 80 ° C. for 14 days is 300% or more,
A joint construction method comprising: a filling step of filling with a one-component room temperature moisture-curing sealant composition having a rate of change in elongation at the maximum load after heating at 80 ° C. for 14 days of 40% or less .