JP2020037643A - Method for manufacturing structure - Google Patents

Abstract

To manufacture a structure using a curable composition excellent in any of production stability, and initial fixing properties when coating a bonding object, and capable of favorably applying even to a material which may deform at a temperature appropriate for a hot-melt adhesive.SOLUTION: The production method of the present invention includes a coating process of coating a member with a curable composition containing a cross-linkable silicon group-containing organic polymer (A), a filler (B), and a curing catalyst (C), and packed in a sealed container. The curing catalyst (C) is represented by the general formula: RRSnO where Rand Rare monovalent hydrocarbon groups respectively, and the viscosity of the curable composition at 23°C, 50% RH is 800 Pa s or more and 4,000 Pa s or less. In the curable composition after activating the curing catalyst (C), the drying time by finger touch when testing a drying time by finger touch of the curable composition under 23°C, 50% RH by JIS A 1439 is 30 sec. or more and 30 min. or less.SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing a structure.

  In recent years, the use of a coating-type curable composition instead of a molded product such as an adhesive tape has been increasing due to its excellent suitability in a production line.

  As a coating-type curable composition for manufacturing a structure such as an architectural use or an automobile use, for example, Patent Document 1 discloses a vinyl polymer having a reactive silicon group at a molecular terminal, a tackifying resin, a filler, and A moisture-curable reactive hot melt adhesive containing a thixotropic agent and a curing catalyst is disclosed.

JP 2009-024108A

  However, since the curable composition described in Patent Document 1 is a moisture-curable reactive hot melt adhesive, it is generally applied while being heated and melted at a high temperature of about 100 to 150 ° C. Therefore, when a structure is manufactured using a material that is relatively weak to heat, there is a possibility that the base material may be deformed or damaged by the application of the adhesive.

  Further, in the production of the structure, sufficient initial fixation is required so that even if a certain degree of vibration or impact is applied at the time of shifting to the next step or during temporary storage, a displacement does not occur. However, a moisture-curable adhesive requires a certain curing time until it is completely cured, and thus it is difficult to satisfy a sufficient initial fixing property and a sufficient curing speed.

  Therefore, the present invention can produce a structure using a curable composition that can be applied at a relatively low temperature (for example, 80 ° C. or lower) and has excellent initial fixability during production of the structure and curability after application. A method is provided.

That is, the present invention relates to the following method for producing a structure and a curable composition for producing a structure.
(1) Coating to apply a curable composition contained in an airtight container, containing (A) a crosslinkable silicon group-containing organic polymer, (B) a filler, and (C) a curing catalyst to a member. Wherein the curing catalyst (C) is represented by the general formula R ⁷ R ⁸ SnO (wherein R ⁷ and R ⁸ are each a monovalent hydrocarbon group), and the curable composition is The viscosity at 23 ° C. and 50% RH is 800 Pa · s or more and 4,000 Pa · s or less, and the curable composition (C) after activating the curing catalyst is based on JIS A 1439. And a touch drying time test of the curable composition at 23 ° C. and 50% RH at a touch drying time of 30 seconds or more and 30 minutes or less.
(2) The method for manufacturing a structure according to (1), wherein the structure is a building.
(3) The method for manufacturing a structure according to (1), wherein the structure is a building member.
(4) The method for producing a structure according to any one of (1) to (3), wherein the curable composition has a viscosity at 80 ° C of 500 Pa · s or more and 2,000 Pa · s or less.
(5) It comprises (A) a crosslinkable silicon group-containing organic polymer, (B) a filler, and (C) a curing catalyst, wherein the (C) curing catalyst has a general formula R ⁷ R ⁸ SnO (wherein , R ⁷ and R ⁸ are each a monovalent hydrocarbon group), and have a viscosity of 800 Pa · s or more and 4,000 Pa · s or less at 23 ° C. and 50% RH, and are activated. In the curable composition containing the curing catalyst (C), a touch dry time test is performed at a temperature of 23 ° C. and a relative humidity of 50% RH in accordance with JIS A1439. A curable composition for producing a structure housed in a closed container.

  According to the present invention, the reactive hot melt adhesive can be appropriately used even for a material that may be deformed or damaged at an optimum temperature, and has an initial fixing property at the time of manufacturing a structure, and curing after application. By using a curable composition having excellent properties, a structure that can withstand long-term use can be manufactured regardless of the material of the material constituting the structure.

  Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments at all, and can be implemented with appropriate modifications within the scope of the present invention. .

<Method of manufacturing structure>
The method for producing a structure of the present invention comprises the steps of: (A) curing a curable composition contained in a closed container containing a crosslinkable silicon-containing organic polymer, (B) a filler, and (C) a curing catalyst. The method includes a coating step of coating the structure.

(Coating process)
The application step is a step of applying the curable composition to an object to be applied. In the application step, the curable composition may be applied at room temperature, or may be applied while being heated to a viscosity suitable for application in a state where air is shut off. When the curable composition is heated in the coating step, the heating temperature is preferably from 30 ° C to 100 ° C, more preferably from 30 ° C to 90 ° C, so that the curable composition can be widely used for heat-fragile materials. , 50 to 80 ° C. However, the heating temperature is higher than the temperature of the surrounding environment at the time of heating.

[Viscosity of curable composition]
(Viscosity at room temperature)
The viscosity of the curable composition at normal temperature (for example, in an environment of 23 ° C. and 50% RH) is from 800 Pa · s to 4,000 Pa · s, preferably from 1,500 Pa · s to 3,500 Pa · s. And more preferably 2,000 Pa · s or more and 3,000 Pa · s or less.

  Since the viscosity of the curable composition in an environment of 23 ° C. and 50% RH is within the above range, the curable composition exhibits a liquid property even in a relatively low temperature range such as room temperature, and the workability is improved. As well as excellent filling properties into containers and initial fixability during structure production. In particular, it is preferable that the viscosity be 2,000 Pa · s or more and 3,000 Pa · s or less, since the balance between workability and initial fixability is excellent.

  If the viscosity of the curable composition at room temperature is too low, the initial fixability after applying the curable composition to an object may be insufficient. On the other hand, if the viscosity of the curable composition at room temperature is excessive, the curable composition may not be able to have a viscosity suitable for application unless the curable composition is heated to a high temperature (for example, 120 ° C. or higher). .

  When the object to be applied is a material that is vulnerable to heat, such as a thermoplastic resin molded article, when applying the curable composition to the object, the heat of the curable composition heated to a high temperature causes the thermoplastic resin molding to be performed. The body or the like may be deformed or the thermoplastic resin molded body or the like may be damaged. Therefore, in manufacturing the structure, different types of curable compositions must be used depending on the material of the application target, and the versatility of the curable composition is inferior. Is preferably lower.

(Viscosity at 80 ° C)
The viscosity at 80 ° C. of the curable composition used in the present invention is from 500 Pa · s to 2,000 Pa · s from the viewpoint of applicability, preferably from 600 Pa · s to 1,500 Pa · s. is there.

  When the viscosity at 80 ° C. of the curable composition is within the above range, the curable composition can be applied to an object without heating the curable composition to a high temperature (for example, 120 ° C. or higher). it can.

[Application method]
The method for applying the curable composition used in the present invention is not particularly limited, and a conventionally known method can be used. Examples of the application method include bead application and point application. Coating can be performed without heating the curable composition to a high temperature, so it can be applied by an extrusion gun to extrude from a container filled with the curable composition, or by continuous automatic production. A method can be used.

(Curable composition)
The curable composition used in the present invention is a moisture-curable composition having high viscosity, excellent production stability, initial fixability after application, and excellent curability, and (A) a crosslinkable silicon group-containing organic compound. A polymer, (B) a filler, and (C) a curing catalyst.

  In order to improve the initial fixability of the curable composition used in the production of the structure, the present inventors have applied the composition to the material constituting the structure, and then immediately set the moisture-curable composition to a high-viscosity state. Considered things.

  It can be applied to materials that are relatively weak to heat. To apply a curable composition to a high-viscosity state immediately after applying the curable composition, use a high-viscosity moisture-curing material at room temperature (for example, 23 ° C.). It is conceivable to apply the composition. However, when a high-viscosity moisture-curable composition is produced using a general production device, unlike the case of a low-viscosity moisture-curable composition, the curing progress during the production is remarkably exhibited, and the container is filled. In some cases, it became difficult, and it was found that there was a problem in manufacturing.

  The reason why the production stability of the high-viscosity moisture-curable composition is reduced is that the high-viscosity composition is easily entrained in air when kneaded in the production apparatus, and is being produced due to the moisture contained in the air. It is also assumed that the curing of the moisture-curable composition proceeds. Therefore, when producing a high-viscosity moisture-curable composition using a general production apparatus, it is considered that the production stability is reduced.

  Therefore, the present inventors have studied a method for producing a curable composition having excellent production stability even when producing a high-viscosity moisture-curable composition using a general production apparatus. As a result, at the time of producing the curable composition, the curable composition is produced using a catalyst having relatively weak activity, and the produced curable composition (containing the catalyst) is filled in a closed container. When the curable composition is heated in a state where the curable composition is sealed in a closed container before use of the curable composition after sealing, the activity of the catalyst is relatively improved, and the curable composition for production of a structure having excellent production stability. It was found that a product was obtained. Therefore, the curable composition used in the present invention is a composition that achieves both the production stability of the curable composition and the initial fixability during structure production.

  In the present invention, the viscosity refers to a value measured at a rotation speed of 10 r / min in a 23 ° C. and 50% RH environment using a B-type viscometer in accordance with JIS K6833-1. Depending on the type of the structure, it is sufficient that the initial fixing property has a sufficient viscosity, but for example, it is 800 Pa · s or more.

[(A) Crosslinkable silicon group-containing organic polymer]
(A) The crosslinkable silicon group of the organic polymer having a crosslinkable silicon group has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and is a group that can be crosslinked by forming a siloxane bond (hereinafter, referred to as “ A component). As the crosslinkable silicon group, for example, a group represented by the general formula (1) is preferable.

In the formula (1), R ¹ represents an organic group. R ¹ is preferably a hydrocarbon group having 1 to 20 carbon atoms. Among them, R ¹ is particularly preferably a methyl group. R ¹ may have a substituent. X represents a hydroxyl group or a hydrolyzable group. When two or more Xs are present, a plurality of Xs may be the same or different. a is an integer of 1, 2 or 3.

  The hydrolyzable group represented by X is not particularly limited, and includes, for example, an alkoxy group, an acyloxy group, a ketoxime group, an aminooxy group, an alkenyloxy group and the like. Among these, an alkoxy group is preferable from the viewpoint of mild hydrolysis and easy handling. Among the alkoxy groups, a group having a smaller number of carbon atoms has higher reactivity, and the reactivity becomes lower 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 use, usually, a methoxy group or an ethoxy group is used.

Examples of the crosslinkable silicon group include a trialkoxysilyl group (—Si (OR ² ) ₃ ) such as a trimethoxysilyl group and a triethoxysilyl group, and a dialkoxysilyl group such as a methyldimethoxysilyl group and a methyldiethoxysilyl group. (—SiR ¹ (OR ² ) ₂ ). Here, R ² is an alkyl group such as a methyl group or an ethyl group. The trialkoxysilyl group is more reactive than the dialkoxysilyl group and can prepare a fast-curing composition. Further, since the dialkoxysilyl group is more stable than the trialkoxysilyl group, a stable composition can be prepared.

  The crosslinkable silicon groups may be used alone or in combination of two or more. The crosslinkable silicon group may be bonded to the main chain or the side chain, or any of them. In the organic polymer of the component (A), the number of crosslinkable silicon groups is preferably 1.0 to 5 on average in one molecule of the organic polymer, and preferably 1.1 to 3. More preferred.

  (A) Examples of the main chain skeleton of the organic polymer having a crosslinkable silicon group include polyoxyalkylene polymers; hydrocarbon polymers such as polyolefin polymers and hydrogenated polyolefin polymers; polyester polymers. Copolymers; vinyl polymers such as (meth) acrylate polymers; and graft polymers obtained by polymerizing vinyl monomers in an organic polymer. These skeletons may be contained alone in the (A) organic polymer having a crosslinkable silicon group, or two or more of them may be contained in blocks or randomly.

  Saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylate polymers have relatively low glass transition temperatures and are obtained cured products. Is preferred because the brittleness is well improved. Polyoxyalkylene polymers and (meth) acrylate polymers are particularly preferred because of their high moisture permeability and excellent deep curability.

The polymer whose main chain skeleton is an oxyalkylene polymer and has a crosslinkable silicon group at the terminal is essentially a polymer having a repeating unit represented by the general formula (2).
-R ³ -O- ··· (2)
(In the formula, R ³ is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 2 to 4 carbon atoms.)

Specific examples of the repeating unit represented by the general formula _{(2), -CH 2 CH 2} O -, - CH 2 CH (CH 3) O -, - CH 2 CH 2 CH 2 CH 2 O- and the like . The main chain skeleton of the polyoxyalkylene polymer having a crosslinkable silicon group 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 containing oxypropylene as a main component is preferable.

  The lower limit of the number average molecular weight of the polyoxyalkylene polymer having a crosslinkable silicon group is preferably 15,000, more preferably 18,000, and still more preferably 20,000. The upper limit of the number average molecular weight is preferably 50,000, more preferably 40,000. The number average molecular weight is a molecular weight in terms of polystyrene measured 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, and if it exceeds 50,000, the viscosity of the composition may increase and the workability may decrease.

  When the content of the crosslinkable silicon group is appropriately reduced in the polyoxyalkylene polymer, the crosslink density in the cured product is reduced, so that the cured product becomes more flexible, the modulus property is reduced and the elongation at break is reduced. growing. In the polyoxyalkylene polymer, the number of crosslinkable silicon groups is preferably 1.2 or more and 2.8 or less, preferably 1.3 or more and 2.6 or less in one molecule of the polymer. More preferably, the number is 1.4 or more and 2.4 or less. If the number of crosslinkable silicon groups contained in the molecule is less than one, the curability will be insufficient, and if it is too large, the network structure will be too dense to exhibit good mechanical properties.

  The polyoxyalkylene polymer having a crosslinkable silicon group may be linear or branched. From the viewpoint of reducing the tensile modulus, the polyoxyalkylene polymer having a crosslinkable silicon group is preferably a linear polymer. The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer having a crosslinkable silicon group is preferably 2 or less, particularly preferably 1.6 or less. In addition, Mw is a weight average molecular weight and Mn is a number average molecular weight.

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

  Other components such as a urethane bond component may be contained in the main chain skeleton of the polyoxyalkylene polymer. Examples of the urethane binding component include aromatic polyisocyanates such as toluene diisocyanate; and components obtained from the reaction of an aliphatic polyisocyanate such as isophorone diisocyanate with a polyoxyalkylene polymer having a hydroxyl group. .

  The introduction of a crosslinkable silicon group into the polyoxyalkylene polymer is based on 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. It is possible by reacting a compound having a reactive functional group and a compound having a crosslinkable silicon group (hereinafter, referred to as a polymer reaction method).

  As an example of the polymer reaction method, a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group is allowed to act on an unsaturated group-containing polyoxyalkylene polymer to form a hydrosilylation or mercapto compound to form a crosslinkable silicon group. A method for obtaining a polyoxyalkylene polymer having the following formula: The unsaturated group-containing polyoxyalkylene polymer can be 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 having reactivity to the functional group. it can.

  Further, as another example of a polymer reaction method, a method of reacting a polyoxyalkylene polymer having a hydroxyl group at a terminal with an isocyanate group, and a compound having a crosslinkable silicon group, or a polyoxy compound having an isocyanate group at a terminal A method of reacting an alkylene polymer with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group can be exemplified. 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) acrylate-based monomer constituting the main chain of the (meth) acrylate-based polymer. For example, (meth) acrylic acid-based monomers; n-butyl (meth) acrylate, stearyl (meth) acrylate-based alkyl ester-based monomers; alicyclic (meth) acrylate-based monomers; (Meth) acrylic ester monomers such as 2-methoxyethyl (meth) acrylate; silyl group-containing (meth) acrylic acids such as γ- (methacryloyloxypropyl) trimethoxysilane Ester monomers and the like.

  In the (meth) acrylate-based polymer, a vinyl-based monomer can be copolymerized together with the (meth) acrylate-based monomer. Examples of the vinyl monomer include styrene, maleic anhydride, and vinyl acetate. Further, as a monomer unit (hereinafter, also referred to as another monomer unit), acrylic acid may be contained in addition to the above.

  These may be used alone or a plurality of them may be copolymerized.

  As a method for producing the (meth) acrylate polymer, for example, a radical polymerization method using a radical polymerization reaction can be used. Examples of the radical polymerization method include a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, and a controlled radical capable of introducing a crosslinkable silicon group into a controlled position such as a terminal. A polymerization method is mentioned.

  Examples of the controlled radical polymerization method include a free radical polymerization method using a chain transfer agent having a specific functional group and a living radical polymerization method. It is preferable to adopt a living radical polymerization method such as atom transfer radical polymerization (ATRP). In addition, as a reaction for synthesizing a polymer whose main chain skeleton is a (meth) acrylate polymer and a part of which is a telechelic polymer (hereinafter, referred to as “pseudo-telechelic polymer”), a crosslinkable Examples include a reaction using a thiol compound having a silicon group, and a reaction using a thiol compound having a crosslinkable silicon group and a metallocene compound.

  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) acrylate polymer having a crosslinkable silicon group. An organic polymer obtained by blending two or more kinds selected from the following can be used. Particularly, an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylate polymer having a crosslinkable silicon group has excellent characteristics.

There are various methods for producing an organic polymer in which a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylate polymer having a crosslinkable silicon group are blended. For example, a compound having a crosslinkable silicon group and a molecular chain substantially having the general formula (3):
—CH ₂ —C (R ⁴ ) (COOR ⁵ ) — (3)
(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an alkyl group having 1 to 5 carbon atoms. Preferably, an alkyl group having 1 to 2 carbon atoms is mentioned. In addition, R ⁵ is a single atom. Or a mixture of two or more types) and a (meth) acrylate monomer unit represented by the general formula (6):
—CH ₂ —C (R ⁴ ) (COOR ⁶ ) — (4)
(Wherein R ⁴ is the same as above, and R ⁶ represents an alkyl group having 6 or more carbon atoms. Preferably, a long-chain alkyl group having 8 to 20 carbon atoms such as a 2-ethylhexyl group and a stearyl group is exemplified. R ⁶ may be used singly or as a mixture of two or more types.) The copolymer comprising a (meth) acrylate monomer unit represented by A method of blending and producing an oxyalkylene polymer is exemplified.

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

  The number average molecular weight of the (meth) acrylate polymer having a crosslinkable silicon group is preferably from 600 to 10,000, more preferably from 1,000 to 5,000, and from 1,000 to 4,500. Is more preferred. By setting the number average molecular weight in this range, the compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group is improved. The (meth) acrylate polymer having a crosslinkable silicon group may be used alone or in combination of two or more. The blending ratio of the polyoxyalkylene polymer having a crosslinkable silicon group and the (meth) acrylate polymer having a crosslinkable silicon group is not particularly limited. The total amount of the (meth) acrylate polymer is preferably in the range of 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, based on 100 parts by mass in total with the polyoxyalkylene polymer. It is more preferably in the range of 15 to 45 parts by mass. If the amount of the (meth) acrylate-based polymer is more than 80 parts by mass, the viscosity becomes high, and the workability deteriorates.

  Further, in the present invention, an organic polymer obtained by blending a saturated hydrocarbon polymer having a crosslinkable silicon group and a (meth) acrylate copolymer having a crosslinkable silicon group can also be used. As a method for producing an organic polymer obtained by blending a (meth) acrylic ester copolymer having a crosslinkable silicon group, there is another method for producing an organic polymer in the presence of an organic polymer having a crosslinkable silicon group. ) A method of polymerizing an acrylate monomer can be used.

[(B) filler]
The filler adjusts the viscosity of the curable composition, secures initial fixability after application of the curable composition, and plays a role in further increasing the adhesiveness and heat resistance of the obtained cured product (hereinafter referred to as B). Component).

  (B) The filler is not particularly limited, and includes, for example, calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, silicic anhydride, calcium silicate, silica (fused silica, precipitated silica), titanium dioxide , Clay, talc, carbon black, slate powder, mica, kaolin, zeolite, diatomaceous earth, clay, wood powder, walnut shell powder, rice husk powder, quartz powder, aluminum powder, zinc powder, asbestos, glass fiber, carbon fiber And the like. Of these, calcium carbonate is preferred, and surface-treated fatty acid-treated calcium carbonate is more preferred.

  Further, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloons, glass balloons, silica balloons, Saran balloons, acrylic balloons, and the like can also be used. Among them, an acrylic balloon is more preferable because the decrease in elongation after curing of the composition is small.

  The fillers may be used alone or in combination of two or more.

  (B) The amount of the filler is not particularly limited, but the viscosity of the curable composition at ordinary temperature (for example, at 23 ° C. and 50% RH environment) is set to 800 Pa · s or more. The amount of the filler is preferably more than 200 parts by mass based on 100 parts by mass of the crosslinkable silicon-group-containing organic polymer (A). In order to suppress the viscosity to 4000 Pa · s or less, the upper limit of the amount of the filler (B) is preferably 500 parts by mass or less, and more preferably 400 parts by mass or less.

  (B) If the compounding amount of the filler is too small, the curable composition may have insufficient initial fixability after being applied to the material constituting the structure.

  On the other hand, if the compounding amount of the filler (B) is too large, the viscosity of the curable composition at room temperature becomes too high, so that it is difficult to suppress curing during production with a general production apparatus, and In some cases, the production stability is poor, or the viscosity suitable for coating may not be attained unless heating at a high temperature (eg, 120 ° C. or higher).

[(C) Curing catalyst]
As the curing catalyst (C), a conventionally known silanol condensation catalyst can be used, and a titanium compound such as an organic tin compound, an alkyl titanate, or an organic silicon titanate, or a bismuth such as bismuth tris 2-ethylhexoate is used. Compounds, tin salts of carboxylic acids such as tin octylate and tin naphthenate: amine salts such as dibutylamine-2-ethylhexoate (hereinafter also referred to as component C). Among these, it is preferable to use an organotin compound.

Among the organic tin compounds, it is particularly preferable to use an organic tin compound represented by the general formula R ⁷ R ⁸ SnO (wherein R ⁷ and R ⁸ are each a monovalent hydrocarbon group).

The monovalent hydrocarbon group for R ⁷ and R ⁸ is not particularly limited. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a dodecyl group, a lauryl group, a propenyl group, a phenyl group and a tolyl group. Preferred examples include hydrocarbon groups having about 1 to 20 carbon atoms, such as a group. R ⁷ and R ⁸ may be the same or different.

As the curing catalyst represented by the general formula R ⁷ R ⁸ SnO, dialkyltin oxide such as dimethyltin oxide, dibutyltin oxide, and dioctyltin oxide is particularly preferable. These curing catalysts may be used alone or in combination of two or more.

When an organotin compound represented by the general formula R ⁷ R ⁸ SnO (hereinafter, also referred to as a heat-activated catalyst) is used, its catalytic activity is low at normal temperature (for example, 23 ° C.), and hardening due to moisture hardly proceeds. However, since the catalytic activity is increased by heating, the production of a highly viscous moisture-curable composition is not a production apparatus that can be completely sealed, but even when a general production apparatus is used, At the time of manufacturing, the progress of curing can be suppressed, and at the time of use (at the time of manufacturing the structure), sufficient curability can be exhibited.

  In addition, in the curable composition used in the present invention, when a heat-activated catalyst is used as the curing catalyst (C), the catalytic activity can be increased by filling the curable composition into a closed container and then heating. In addition, it is possible to obtain a composition having a viscosity sufficient for initial fixation at the time of manufacturing a structure while suppressing the viscosity at the time of manufacturing the curable composition to a viscosity suitable for the manufacturing.

  The compounding amount of the (C) curing catalyst is preferably from 0.1 to 10 parts by mass, more preferably from 1 to 5 parts by mass, per 100 parts by mass of the (A) crosslinkable silicon-containing organic polymer. More preferred. (C) If the compounding amount of the curing catalyst is less than 0.1 part by mass, it takes a long time to cure, and thus, at the time of manufacturing the structure, it may affect the transition to the next step, and exceeds 10 parts by mass. And the pot life may be insufficient.

[Other additives]
The curable composition according to the present invention may further comprise, as necessary, a diluent, a plasticizer, a silane coupling agent, a dehydrating agent (storage stability improver), a tackifier, and an anti-sagging agent, in addition to the components described above. , An ultraviolet absorber, an antioxidant, a flame retardant, a colorant, a radical polymerization initiator, and the like, and may be blended with another compatible polymer.

(Diluent)
The diluent is added for the purpose of adjusting the viscosity of the curable composition and the workability in the step of applying the curable composition.

  As the diluent, a general organic solvent having a boiling point of 250 ° C. or less can be suitably used, but a diluent which volatilizes during the curing process of the curable composition and finally hardly remains in the cured product is preferred. As the diluent, conventionally known compounds can be used, and there is no particular limitation, but a saturated hydrocarbon solvent; an aromatic hydrocarbon solvent; an ester solvent; a ketone solvent; an alcohol solvent; Is mentioned. The diluents may be used alone or in combination of two or more.

(Plasticizer)
The plasticizer is added for the purpose of increasing the elongation properties of the cured product or reducing the modulus. As the plasticizer, conventionally known compounds can be used, and there is no particular limitation. Phosphoric acid esters; phthalic acid esters; fatty acid monobasic acid esters; fatty acid dibasic acid esters; glycol esters; Group plasticizers; polyester plasticizers; polyethers; polystyrenes, acrylic plasticizers, and the like. The plasticizers may be used alone or in combination of two or more.

(Silane coupling agent)
The silane coupling agent is added for the purpose of improving the adhesiveness of the curable composition and promoting curing. As the silane coupling agent, a conventionally known compound can be used and is not particularly limited. For example, aminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylamino Aminosilanes such as propylmethylmethoxysilane, epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like Mercaptosilanes, isocyanate silanes such as γ-isocyanatopropyltrimethoxysilane and the like can be mentioned. These silane coupling agents may be used alone or in combination of two or more.

(Dehydrating agent)
The dehydrating agent is added for the purpose of removing water during storage. As the dehydrating agent, conventionally known compounds can be used, and there is no particular limitation. For example, silane compounds such as vinyltrimethoxysilane, dimethyidimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane Is mentioned.

(Tackifier)
The tackifier can be added for the purpose of improving the initial fixability. As the tackifier, conventionally known compounds can be used, and there is no particular limitation. Terpene resins, aromatic modified terpene resins, hydrogenated terpene resins obtained by hydrogenating the terpene resins, and terpenes copolymerized with phenols. Terpene-phenol resin, phenol resin, modified phenol resin, xylene-phenol resin, cyclopentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene Base resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, DCPD resin and the like. These may be used alone or in combination of two or more.

  In the curable composition used in the present invention, it is preferable not to add a tackifier, since heat creep resistance may be reduced. The amount is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 1 part by mass or less based on 100 parts by mass of the crosslinkable silicon group-containing organic polymer.

(Antioxidant)
The antioxidant is a compound used to prevent oxidation of the cured product and improve weather resistance, and a conventionally known compound can be used, and is not particularly limited. Examples thereof include a hindered amine and a hindered amine. Phenolic antioxidants and the like can be mentioned. Antioxidants may be used alone or in combination of two or more.

(UV absorber)
The ultraviolet absorber is a compound used for preventing light deterioration of a cured product and improving weather resistance, and a conventionally known compound can be used. There is no particular limitation, for example, a benzotriazole-based compound, UV absorbers such as triazine-based, benzophenone-based, and benzoate-based ultraviolet absorbers. The ultraviolet absorbers may be used alone or in combination of two or more.

(Production method of curable composition)
The method for producing a curable composition according to the present invention includes a mixing step and a container filling step. Furthermore, the method for producing a curable composition according to the present invention includes, for example, a catalyst activation step before the curable composition is actually used.

[Mixing process]
In the mixing step, the above-mentioned component (A), a crosslinkable silicon-containing organic polymer, (B) a filler, (C) a curing catalyst, and, if necessary, an additive are mixed by a conventionally known method. And a step of preparing a curable composition. The mixing step does not require the use of a completely sealable mixing apparatus, and can be performed even in the presence of air. However, this does not exclude the use of a completely sealable mixing device.

[Container filling process]
The container filling step is a step of filling the curable composition prepared in the above-described mixing step into a closed container. The filling method may be a conventionally known method, and is not particularly limited.

[Closed container]
The curable composition described above is filled in a closed container. (A) The crosslinkable silicon group of the crosslinkable silicon group-containing organic polymer undergoes crosslinking and cures due to moisture in the air. Therefore, in order to ensure storage stability, the curable composition is preferably housed in a closed container.

  The shape of the closed container is not particularly limited as long as the curable composition can be closed, and may be selected according to the use. For example, a pail can that can store 3 to 50 L of the curable composition, a cartridge container that can store less than 1 L of the curable composition, and the like can be given.

[Catalytic activation step]
The catalyst activation step is a step of increasing the activity of the component (C) curing catalyst in the curable composition.

  (C) As an example of activation of a curing catalyst, a curable composition filled in a closed container and sealed is placed in an environment of 30 ° C to 150 ° C, preferably 50 to 150 ° C, more preferably 70 to 120 ° C. Heating for 1 to 6 days, preferably 1 to 4 days is mentioned.

  The heating temperature and the heating time may be appropriately adjusted depending on the filling form of the curable composition and the type of the curing catalyst. For example, a pail can having a capacity of 20 L is preferably at about 90 ° C. for 4 days, and a cartridge vessel having a capacity of 333 mL is preferably at about 100 ° C. for about 1 day.

  In general, when the heating temperature exceeds 150 ° C., the curable composition tends to deteriorate, and when the heating temperature is less than 30 ° C., the heating time required for activating the curing catalyst becomes long, resulting in poor production efficiency of the curable composition. May be.

  In addition, when the curable composition is heated more than necessary, the composition deteriorates, and the performance may change from the expected performance. It is preferable to return the curable composition to room temperature as it is from the viewpoint of the stability of the performance of the curable composition.

  In the present invention, according to JIS A 1439, the curable composition before the catalytic activity step when the curable composition under the dry contact time test of the curable composition at 23 ° C. and 50% RH is: An appropriate time may be ensured depending on the manufacturing apparatus to be used, but it is preferably, for example, 2 hours or more, and particularly preferably 3 hours or more. In addition, the curable composition after the catalyst activation step has a touch dry time of 30 seconds or more when the curable composition is subjected to a dry test under a temperature of 23 ° C. and 50% RH in accordance with JIS A1439. The time is 30 minutes or less, preferably 1 minute or more and 20 minutes or less, more preferably 3 minutes or more and 15 minutes or less. When the touch-drying time is within the above range, the production stability is excellent, and at the time of use, the curability is fast, and the initial fixability is also excellent.

(Application target)
The curable composition produced by the above-mentioned [Method for producing curable composition] is used for applying to a target member.

  In the present invention, the shape and material of the application target in manufacturing the structure are not particularly limited.

  The method for manufacturing a structure according to the present invention is not particularly limited as long as it is an application requiring initial fixation, and may be applied to, for example, architectural applications (sealing to joints of buildings, manufacturing of building members, and the like). ) And in the manufacture of automobiles. Further, the curable composition used in the present invention can be suitably used as an adhesive, a sealing material, a potting material, a coating agent and the like.

(Effects of Embodiment)
The curable composition according to the present invention can be appropriately used even for a material that can be deformed or damaged at the optimum temperature (more than 100 ° C., for example, about 120 ° C.) of the reactive hot melt adhesive. . Further, in the present invention, since the catalyst activity of the curing catalyst (C) is low before heating, the viscosity of the curable composition can be suppressed to a viscosity suitable for the production at the time of producing the curable composition, and the structure can be reduced. By heating before the production of the body or the like to increase the catalytic activity of the curing catalyst (C), a curable composition having a viscosity sufficient for the initial fixation of the structure can be obtained. Thereby, according to the curable composition according to the present invention, since the curable composition exhibits initial fixing property and is excellent in curability after application at the time of production of the structure, it can be used for a long time regardless of the material of the material constituting the structure. It is possible to manufacture a structure that can withstand the above.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these descriptions.

<Preparation of curable composition>
In Examples and Comparative Examples, each component was mixed at the composition and mass ratio shown in Table 1.

In Table 1, each component is as follows.
(A) Crosslinkable silicon-group-containing organic polymer * 1: A1 component, a copolymer of a polymer having a main chain of polyoxypropylene and a methyldimethoxysilyl group at a molecular terminal and a polymer of a main chain having a polymethacrylic acid ester in the molecule. With a polymer having a methyldimethoxysilyl group (Product name: Silyl MA440, manufactured by Kaneka Corporation)
* 2: A2 component, a polymer whose main chain is polypropylene oxide and has a crosslinkable silicon group as a reactive group (Product name: MS Polymer S327, manufactured by Kaneka Corporation)
(B) Filler * 3: Heavy calcium carbonate (Product name: Whiten SB, manufactured by Shiroishi Calcium Co., Ltd.)
* 4: Colloidal calcium carbonate (Product name: Calfine 500, manufactured by Maruo Calcium Co., Ltd.)
(C) Specific curing catalyst * 5: Dioctyltin oxide (product name: U-800P, manufactured by Nitto Kasei Corporation)
* 6: Dibutyltin oxide (product name: U-300, manufactured by Nitto Kasei Corporation)
(C ') Other curing catalyst * 7: Dioctyltin dinedecanoate (product name: U-830, manufactured by Nitto Kasei Co., Ltd.)
* 8: Dibutyltin dilaurate (product name: MSCAT-02, manufactured by Nitto Kasei Corporation)
(D) Additive * 9: Diluent, normal paraffin (product name: N-11, manufactured by JX Energy Corporation)
* 10: Plasticizer, polyoxypropylene triol (product name: S3011, manufactured by Asahi Glass Co., Ltd.)
* 11: Silane coupling agent, 3-aminopropyltrimethoxysilane (product name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Evaluation>
The initial fixability, the viscosity, the curability of the curable composition before the catalytic activation step (production stability), and the curability after the catalytic activation step of the curable compositions of Examples and Comparative Examples were evaluated as follows.

(Initial fixation)
The curable compositions in the sealed containers (cartridges) of Examples 1 to 5 and Comparative Examples 1 to 3 were heated in a 100 ° C environment for 1 day, and kept in a sealed state at 23 ° C and 50% RH for 24 hours. It was left still. Thereafter, the curable composition heated to 80 ° C. was applied to an aluminum plate (25 mm wide × 100 mm long × 1.6 mm thick) with an application area of 25 mm wide × 25 mm long, and immediately the same type of aluminum I glued it to the board. After the bonded test pieces were cured at 23 ° C. and 50% RH for 10 minutes, a tensile shear strength test was performed at a test speed of 500 mm / min according to JIS K6850. Table 1 shows the results.

〔viscosity〕
[Viscosity at 23 ° C. and 50% RH]
The curable compositions according to Examples 1 to 5 and Comparative Example 1 were respectively prepared at the compounding ratios shown in Table 1, filled in a sealed container (a cartridge container having a capacity of 333 mL), sealed, and then placed in a 100 ° C environment. The mixture was heated for one day, and left standing at 23 ° C. and 50% RH for 24 hours in a sealed state. Thereafter, the curable composition was taken out of the closed container, and the viscosity of the composition was measured at 23 ° C. and 50% RH using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., TVB10 viscometer No. 7 rotor, rotation speed: 10 rpm, (Measurement time: 60 seconds). Table 1 shows the results.

  Further, the curable compositions according to Comparative Examples 2 and 3 were prepared at the compounding ratios shown in Table 1, respectively, filled in a closed container (a cartridge container having a capacity of 333 mL), sealed, and then placed at 23 ° C. and 50% RH. It was left standing for 24 hours. Thereafter, the curable composition was taken out of the closed container, and the viscosity of the composition was measured at 23 ° C. and 50% RH using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., TVB10 viscometer No. 7 rotor, rotation speed: 10 rpm, (Measurement time: 60 seconds). Table 1 shows the results.

[Viscosity at 80 ° C]
The curable compositions according to Examples 1 to 5 and Comparative Example 1 were respectively prepared at the compounding ratios shown in Table 1, filled in a closed container (a cartridge container having a capacity of 333 mL), and sealed to obtain a curable composition of 100%. The mixture was heated at 23 ° C and 50% RH at 23 ° C except that the container was heated to 80 ° C with the sealed container kept at 23 ° C and 50% RH for 24 hours. The viscosity was measured in the same manner. Table 1 shows the results.

  In addition, the curable compositions according to Comparative Examples 2 and 3 were also prepared at the compounding ratio shown in Table 1, filled in a closed container (a cartridge container having a capacity of 333 mL), sealed, and sealed at 23 ° C and 50% RH for 24 hours. After standing for a period of time, the viscosity was measured by the same method as the viscosity at 23 ° C. and 50% RH except that the whole of the sealed container was heated to 80 ° C. Table 1 shows the results.

[Curability before catalyst activation step] (Production stability)
The curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were filled in a sealed container (a cartridge container having a capacity of 333 mL), sealed, and allowed to stand at 23 ° C. and 50% RH for 24 hours, followed by JIS A 1439. In accordance with the test, the touch dry time test was performed at 23 ° C. and 50% RH. Table 1 shows the measurement results of the touch dry time.

(Curability after catalyst activation step)
The curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were filled in a sealed container (a cartridge container having a capacity of 333 mL), sealed, heated in a 100 ° C. environment for 24 hours, and then kept in a sealed state. The mixture was allowed to stand at 23 ° C. and 50% RH for 24 hours. According to JIS A 1439, a touch dry time test was performed at 23 ° C. and 50% RH. Table 1 shows the measurement results of the touch dry time.

<Result>
In Examples 1 to 5 using (C) a curing catalyst that exhibits high activity by heating, the production stability was higher than Comparative Examples 1 and 2 using a curing catalyst having sufficient activity without requiring activation of the catalyst. It was excellent. In addition, although the (C) curing catalyst which expresses high activity by heating is used, in Comparative Example 3 in which the viscosity at 23 ° C. and 50% RH after activation of the catalyst is less than 800 Pa · s, Fixation was insufficient.

Claims (5)

An application step of applying a curable composition contained in an airtight container, containing (A) a crosslinkable silicon group-containing organic polymer, (B) a filler, and (C) a curing catalyst to a member. ,
The curing catalyst (C) is represented by a general formula R ⁷ R ⁸ SnO (wherein R ⁷ and R ⁸ are each a monovalent hydrocarbon group),
The viscosity of the curable composition at 23 ° C. and 50% RH is 800 Pa · s or more and 4,000 Pa · s or less,
(C) In the curable composition after activating the curing catalyst, the touch-drying time test of the curable composition at 23 ° C. and 50% RH was performed in accordance with JIS A1439. A method for producing a structure, wherein a touch drying time is 30 seconds or more and 30 minutes or less.   The method for manufacturing a structure according to claim 1, wherein the structure is a building.   The method for manufacturing a structure according to claim 1, wherein the structure is a building member.   The method according to claim 1, wherein the curable composition has a viscosity at 80 ° C. of 500 Pa · s or more and 2,000 Pa · s or less. (A) a crosslinkable silicon group-containing organic polymer, (B) a filler, and (C) a curing catalyst,
The curing catalyst (C) is represented by a general formula R ⁷ R ⁸ SnO (wherein R ⁷ and R ⁸ are each a monovalent hydrocarbon group),
The viscosity at 23 ° C. and 50% RH is 800 Pa · s or more and 4,000 Pa · s or less,
In the curable composition containing the activated curing catalyst (C), the touch dry time was 30 seconds when the touch dry time test was performed at 23 ° C. and 50% RH in accordance with JIS A1439. More than 30 minutes
A curable composition for producing a structure housed in a closed container.