WO2022075386A1

WO2022075386A1 - Curable composition

Info

Publication number: WO2022075386A1
Application number: PCT/JP2021/037076
Authority: WO
Inventors: 雄板野; 正臣坂部; 史佳山澤; 幸平細見
Original assignee: 株式会社カネカ
Priority date: 2020-10-08
Filing date: 2021-10-07
Publication date: 2022-04-14
Also published as: CN116234874A; CN116234874B; JPWO2022075386A1

Abstract

The present invention addresses the problem of providing a new curable composition having excellent initial fixing properties. A curable composition comprising: 100 parts by weight of an organic polymer (A) having a hydrolyzable silicon group; 10-500 parts by weight of a polyvinylchloride resin (B); and 150-500 parts by weight of calcium carbonate (C), wherein the most frequent size of the polyvinylchloride resin (B) is 0.1-0.5 μm.

Description

Curable composition

The present invention relates to a curable composition.

The "organic polymer having a hydrolyzable silicon group" can be crosslinked by forming a siloxane bond accompanied by a hydrolysis reaction of the hydrolyzable silicon group due to moisture or the like even at room temperature to obtain a rubber-like cured product. It is known that it has the property of. Polyoxyalkylene-based polymers having a hydrolyzable silicon group have already been industrially produced and are widely used as raw material resins for applications such as sealants, adhesives and paints.

For example, Patent Document 1 discloses a curable composition comprising 100 parts by weight of an organic polymer having at least one hydrolyzable silicon group in the molecule and 10 to 500 parts by weight of a vinyl resin.

Further, Patent Document 2 contains 100 parts by weight of an organic polymer having at least one hydrolyzable silicon group in the molecule, 10 to 500 parts by weight of a vinyl resin, and 1 to 150 parts by weight of a polymer plasticizer. The curable composition is disclosed.

Japanese Unexamined Patent Publication No. 63-225654 Japanese Unexamined Patent Publication No. 2-102237

However, the above-mentioned conventional technology is not sufficient from the viewpoint of initial fixing, and there is room for further improvement.

One embodiment of the present invention has been made in view of the above problems, and an object thereof is to provide a novel curable composition having excellent initial fixing property.

The present inventors have diligently studied to solve the above-mentioned problems. As a result, the curable composition containing a specific amount of each of an organic polymer having a hydrolyzable silicon group, calcium carbonate, and a polyvinyl chloride resin having a specific most frequent diameter is uniquely excellent in initial fixing property. The present invention was completed.

That is, the curable composition according to the embodiment of the present invention comprises 100 parts by weight of an organic polymer (A) having a hydrolyzable silicon group, 10 parts by weight to 500 parts by weight of a polyvinyl chloride resin (B), and calcium carbonate. (C) Contains 150 parts by weight to 500 parts by weight, and the most frequent diameter of the polyvinyl chloride resin (B) is 0.10 μm to 0.50 μm.

According to one embodiment of the present invention, there is an effect that a novel curable composition having excellent initial fixing property can be provided.

An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope of the claims. The technical scope of the present invention also includes embodiments or examples obtained by appropriately combining the technical means disclosed in different embodiments or examples. Further, by combining the technical means disclosed in each embodiment, new technical features can be formed. In addition, all the academic documents and patent documents described in the present specification are incorporated as references in the present specification. Further, unless otherwise specified in the present specification, "A to B" representing a numerical range is intended to be "A or more (including A and larger than A) and B or less (including B and smaller than B)".

[1. Technical Idea of One Embodiment of the Present Invention]
The present inventors have made diligent studies to develop a curable composition having excellent initial fixing property, for example, an adhesive having excellent initial fixing property.

Adhesives with excellent initial fixing properties are sometimes called high-tuck adhesives. An adhesive having excellent initial fixability exhibits excellent fixability (adhesiveness) even immediately after being taken out of the container. Therefore, an adhesive having excellent initial fixing property is preferably used in the construction of the interior of a building, for example, when a heavy glass plate or a decorative panel is fixed to a vertical surface such as a wall surface.

Not only the viscosity of the curable composition but also the thixotropic property can affect the initial fixing property of the curable composition. That is, in order to improve the initial fixing property of the curable composition, it is necessary to have both the viscosity of the curable composition and the thixotropic property, and it is not enough to simply increase the viscosity of the curable composition. Therefore, in order to improve the initial fixing property of the curable composition, many studies are required both qualitatively and quantitatively.

As described above, the techniques described in Patent Documents 1 and 2 are not sufficient from the viewpoint of initial fixing, and there is room for further improvement. In other words, the techniques described in Patent Documents 1 and 2 are not techniques related to high-tack adhesives, and do not provide useful information for the development of adhesives having excellent initial fixing properties, which are required by the present inventors. rice field. Therefore, the present inventors have made diligent studies to develop an adhesive having excellent initial fixing property without relying on the technical contents described in Patent Documents 1 and 2. As a result, the present inventors independently found the following findings and completed the present invention: an organic polymer having a hydrolyzable silicon group, calcium carbonate, and polyvinyl chloride having a specific most frequent diameter. A curable composition containing a specific amount of vinyl resin is excellent in initial fixing property.

[2. Curable composition]
The curable composition according to one embodiment of the present invention comprises 100 parts by weight of an organic polymer (A) having a hydrolyzable silicon group, 10 parts by weight to 500 parts by weight of a polyvinyl chloride resin (B), and calcium carbonate (C). ) It contains 150 parts by weight to 500 parts by weight, and the most frequent diameter of the polyvinyl chloride resin (B) is 0.10 μm to 0.50 μm.

In the present specification, the "curable composition according to one embodiment of the present invention" may be hereinafter referred to as "the present curable composition", and is "an organic polymer (A) having a hydrolyzable silicon group". May be hereinafter referred to as "organic polymer (A)".

Since the present curable composition has the above-mentioned structure, it has an advantage of being excellent in initial fixing property. Further, since the present curable composition has the above-mentioned structure, it also has an advantage of being excellent in storage stability. Further, since the present curable composition has the above-mentioned structure, it is possible to provide a curable composition having excellent initial fixing property even when the amount of the organic polymer (A) is small. Therefore, the present curable composition also has the advantages of being inexpensive and economical.

[2-1. Organic polymer (A)]
The organic polymer (A) is a polymer containing a hydrolyzable silicon group at the molecular end. The hydrolyzable silicon group is a functional group in which a reactive group such as an alkoxy group, a halogen atom, an acyloxy group, an alkenyloxy group, an amide group and an oxime group is bonded to a silicon group (Si group). The "hydrolyzable silicon group" may also be referred to as a "reactive silicon group", a "crosslinkable silicon group", a "hydrolyzable silyl group", a "reactive silyl group" or a "crosslinkable silyl group". be.

Specific examples of the hydrolyzable silicon group include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group and a dimethoxyethylsilyl group. Group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) dimethoxysilyl group, and ( N, N-diethylaminomethyl) diethoxysilyl group and the like can be mentioned, but the present invention is not limited thereto. Among these, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, and (methoxymethyl) diethoxysilyl group show high activity. , It is preferable because a cured product having good mechanical properties can be obtained. Since it exhibits high activity, a trimethoxysilyl group, a (chloromethyl) dimethoxysilyl group, and a (methoxymethyl) dimethoxysilyl group are particularly preferable. Methyldimethoxysilyl group, methyldiethoxysilyl group, and triethoxysilyl group are particularly preferable because of their excellent stability. Methyldiethoxysilyl groups and triethoxysilyl groups are particularly preferred because of their high safety. The trimethoxysilyl group, triethoxysilyl group, and dimethoxymethylsilyl group are particularly preferable because they are easy to produce.

The organic polymer (A) preferably has an average of 1.2 to 5.0 hydrolyzable silicon groups per molecule, more preferably 1.2 to 4.0. It is more preferable to have 1.2 to 3.0 pieces. When the organic polymer (A) has 1.2 or more hydrolyzable silicon groups per molecule on average, a curable composition having good curability can be provided. Therefore, in the cured product that the curable composition can provide, good rubber elasticity is obtained, and the resilience, durability, and / or creep resistance of the cured product are improved. The hydrolyzable silicon group may be at the main chain end or the side chain end of the organic polymer (A), or may be at both the main chain end and the side chain end. In particular, when the hydrolyzable silicon group is present only at the end of the main chain of the organic polymer (A), the effective network length in the finally formed cured product becomes long, so that the strength and elongation are high. Moreover, it is preferable because a rubber-like cured product having a low elastic modulus can be easily obtained.

The method for introducing the hydrolyzable silicon group into the organic polymer may be a known method. For example, the following methods I to III can be mentioned.

Method I: An organic polymer having a functional group such as a hydroxyl group is reacted with a compound having an unsaturated group and an active group exhibiting reactivity with the functional group to obtain an organic polymer having an unsaturated group. Then, the obtained organic polymer having an unsaturated group is reacted with a hydrosilane compound having a hydrolyzable silicon group by hydrosilylation.

Examples of the compound having an unsaturated group used in Method I and an active group exhibiting reactivity with the functional group include unsaturated group-containing epoxy compounds such as allyl chloride, methallyl chloride, and allyl glycidyl ether. I can give it.

Examples of the hydrosilane compound used in Method I include, but are not limited to, halogenated silanes, alkoxysilanes, asyloxysilanes, and ketoximatesilanes.

Examples of the halogenated silanes include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane.

Examples of the alkoxysilanes include dialkoxysilanes and trialkoxysilanes. More specifically, as alkoxysilanes, trimethoxysilane, triethoxysilane, triisopropoxysilane, 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane, di Examples thereof include ethoxymethylsilane, dimethoxymethylsilane, and phenyldimethoxysilane.

Examples of the acyloxysilanes include methyldiacetoxysilane and phenyldiacetoxysilane.

Examples of the ketoximatesilanes include bis (dimethylketoximate) methylsilane and bis (cyclohexylketoximate) methylsilane.

Among these hydrosilane compounds, dialkoxysilanes are (a) easy to proceed with the hydrosilylation reaction and (b) excellent in the balance between the storage stability and the hydrolysis rate of the obtained reaction product. And trialkoxysilanes are preferable, and dimethoxymethylsilane, trimethoxysilane, and triethoxysilane are more preferable.

Method II: An organic weight having an unsaturated group obtained by subjecting a compound having a mercapto group and a hydrolyzable silicon group to a radical addition reaction in the presence of a radical initiator and / or a radical source in the same manner as in Method I. Examples include a method of introducing into an unsaturated radical site of coalescence.

Examples of the compound having a mercapto group and a hydrolyzable silicon group used in Method II include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane. It can, but is not limited to these.

Method III: A compound having a hydrolyzable silicon group and a functional group exhibiting reactivity with the functional group is reacted with an organic polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule.

As a method of reacting an organic polymer having a hydroxyl group with a compound having a hydrolyzable silicon group and an isocyanate group exhibiting a hydroxyl group in Method III, for example, Japanese Patent Application Laid-Open No. 3-47825 is shown. However, the method is not limited to this.

Examples of the compound having an isocyanate group reactive with a hydrolyzable silicon group and a hydroxyl group used in Method III include γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and isocyanatemethyltrimethoxysilane. Examples thereof include, but are not limited to, isocyanate methyltriethoxysilane and isocyanatemethyldimethoxymethylsilane.

Among the above methods I and III, the method of reacting an organic polymer having a hydroxyl group at the terminal with a hydrolyzable silicon group and a compound having an isocyanate group exhibiting reactivity with a hydroxyl group is relatively short. It is preferable because a high conversion rate can be obtained in the reaction time. On the other hand, the organic polymer having a hydrolyzable silicon group obtained by Method I has a lower viscosity than the organic polymer having a hydrolyzable silicon group obtained by Method III, and is a curable composition having good workability. Is obtained. Further, the organic polymer having a hydrolyzable silicon group obtained by Method II may have a strong odor based on mercaptosilane. Therefore, method I is particularly preferable.

The main chain skeleton of the organic polymer (A) (also simply referred to as the main chain) is not particularly limited. The main chain skeleton of the organic polymer (A) is, for example, (a) a polyoxyalkylene polymer containing a repeating unit derived from an alkylene oxide, (b) an ether / ester block copolymer, and (c) a vinyl-based monomer. Examples thereof include a vinyl-based polymer containing a repeating unit derived from, and (d) a diene-based polymer containing a repeating unit derived from a diene-based monomer. Among these, the main chain skeleton of the organic polymer (A) preferably contains a polyoxyalkylene polymer, and more preferably a polyoxyalkylene polymer. According to this configuration, the curable composition has the advantage of exhibiting good adhesion to various types of adherends (sometimes referred to as substrates or adherends).

Examples of the repeating unit contained in the polyoxyalkylene polymer include a polyoxyethylene unit, a polyoxypropylene unit, a polyoxybutylene unit, and the like, and a polyoxypropylene unit is preferable. The repeating unit contained in the polyoxyalkylene polymer may be one or more selected from the group consisting of (a) polyoxyethylene units, polyoxypropylene units and polyoxybutylene units (b). ) It may contain one kind or two or more kinds of polyoxyalkylene units other than the above group.

Examples of the method for synthesizing the polyoxyalkylene polymer include (a) a polymerization method using an alkali catalyst such as KOH, and (b) an organic aluminum compound shown in JP-A-61-215623 and porphyrin. Transition metal compound such as a (E) A polymerization method using a composite metal cyanide complex catalyst (for example, a zinc hexacyanocobaltate glyme complex catalyst) shown in (d), and (d) a polymerization method using a catalyst consisting of a polyphosphazene salt shown in JP-A-10-273512. Examples thereof include, but are not limited to, a polymerization method using a catalyst composed of a phosphazene compound shown in JP-A-11-060722. Among these synthetic methods, a polymerization method in which an alkylene oxide is reacted with an initiator in the presence of a composite metal cyanide complex catalyst is preferable because a polymer having a narrow molecular weight distribution can be obtained.

Examples of the complex metal cyanide complex catalyst include Zn ₃ [Co (CN) ₆ ] ² (zinc hexacyanocovalent complex). Further, a catalyst in which an alcohol and / or ether is coordinated as an organic ligand to a zinc hexacyanocobaltate complex or the like can also be used.

As the initiator, "a compound having at least one active hydrogen group" (hereinafter, also referred to as "active hydrogen-containing compound") is preferable. The active hydrogen-containing compound includes (a) alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, allyl alcohol, methanol, ethanol, propanol, butanol, pentanol, and hexanol, and (b) a number average molecular weight of 500 to 20,000. Examples include linear and / or branched polyether compounds.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, and isobutylene oxide.

The organic polymer (A) in one embodiment of the present invention may be linear or branched. The organic polymer (A) in one embodiment of the present invention is preferably a mixture of a linear organic polymer (A1) and a branched organic polymer (A2). According to this structure, the curable composition has an advantage that it can provide a cured product having excellent both high shear strength and high breaking elongation, that is, a cured product (adhesive layer) which is resistant to impact and vibration and has excellent durability. Has. In other words, if the organic polymer (A) is a mixture of a linear organic polymer (A1) and a branched organic polymer (A2), the resulting effective composition will be impact and It is resistant to vibration and can be suitably used as an adhesive having excellent durability.

In one embodiment of the present invention, a case where the organic polymer (A) is a mixture of a linear organic polymer (A1) and a branched organic polymer (A2) will be described. In this case, the weight ratio of the linear organic polymer (A1) to the branched organic polymer (A2) in the organic polymer (A) (weight of the organic polymer (A1) / organic polymer (A2)). The weight) is not particularly limited, but is preferably 0.1 to 9.0, more preferably 0.3 to 5.0, and further preferably 0.4 to 4.0. It is preferably 1.0 to 3.0, and particularly preferably 1.0 to 3.0. According to this configuration, the curable composition can provide a cured product (adhesive layer) that is superior in both high shear strength and high breaking elongation, in other words, resistant to impact and vibration, and excellent in durability. It has the advantage of.

The number average molecular weight (Mn) of the organic polymer (A) is a value measured by gel permeation chromatography (GPC) (polystyrene equivalent), and is preferably 1,000 to 100,000, 2. 000 to 50,000 is more preferable, and 3,000 to 35,000 is particularly preferable. If the number average molecular weight is (a) less than 1,000, the elongation of the cured product tends to be insufficient, and if it exceeds (b) 100,000, the curable composition becomes highly viscous. In addition, it tends to be inconvenient in terms of workability. The molecular weight distribution (Mw / Mn) of the organic polymer (A) measured by GPC is preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.4 or less, and 1.3 or less. It is particularly preferable, and 1.2 or less is most preferable.

As the organic polymer (A), a commercially available product can also be used. For example, (a) Kaneka Corporation, product name: Kaneka MS Polymer, and product name: Kaneka Cyril, (b) AGC Co., Ltd., product name: Exester, (c) Wacker, product name: GENIOSIL. , Etc. have already been manufactured and sold for industrial use, and can be easily obtained and used as the organic polymer (A).

The content of the organic polymer (A) in the present curable composition is not particularly limited. The content of the organic polymer (A) in the present curable composition is preferably 10% by weight to 25% by weight, preferably 11% by weight to 24% by weight, based on 100% by weight of the curable composition. More preferably, it is 12% by weight to 23% by weight, more preferably 13% by weight to 22% by weight, further preferably 14% by weight to 21% by weight, and further preferably 15% by weight to 20% by weight. It is particularly preferable to be% by weight. According to this configuration, the curable composition is inexpensive and therefore has the advantage of being economically superior.

[2-2. Polyvinyl chloride resin (B)]
As used herein, the term "polyvinyl chloride resin" is intended to be a resin having 50 mol% or more of structural units derived from vinyl chloride in 100 mol% of the structural units constituting the resin.

As a result of diligent studies, the present inventors have independently found the following findings: (a) When the curable composition contains the polyvinyl chloride resin (B), the viscosity of the curable composition is significantly increased. The viscous property of the curable composition can be improved without the need for; and (b) the curable composition contains the polyvinyl chloride resin (B) and calcium carbonate, whereby the organic polymer (b) is used in the curable composition. A) A. A wide range of concentration ranges, the rheological behavior suitable for high-tack adhesives should be exhibited.

The polyvinyl chloride resin (B) may be (a) a vinyl chloride homopolymer composed only of structural units derived from vinyl chloride, and (b) vinyl chloride and chloride copolymerizable with vinyl chloride. It may be a copolymer with a monomer other than vinyl (hereinafter, also referred to as monomer A). The polyvinyl chloride resin (B) may have a structural unit derived from vinyl chloride and a structural unit derived from the monomer A.

Examples of the monomer A include vinyl acetate, vinylidene chloride, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, maleic acid, maleic acid ester, acrylonitrile and the like.

The degree of polymerization of the polyvinyl chloride resin (B) is not particularly limited, but for example, the average degree of polymerization is preferably 200 to 10000, and more preferably 300 to 4000.

In the present specification, the "most frequent diameter of the polyvinyl chloride resin (B)" is the most frequent obtained when the particle diameter of the primary particles of the polyvinyl chloride resin (B) is expressed by a frequency distribution on a volume basis. Intended for diameter. The "mode diameter" is sometimes referred to as the "mode diameter". The most frequent diameter of the primary particles of the polyvinyl chloride resin (B) is, for example, a disk centrifugal particle using a latex containing the polyvinyl chloride resin (B) obtained in the manufacturing process of the polyvinyl chloride resin (B) as a sample. It can be obtained by measurement using a diameter distribution measuring device (CPS Disc Centrifuge manufactured by CPS Instruments). In other words, the "mode of the polyvinyl chloride resin (B)" can be said to be the "mode of the primary particles of the polyvinyl chloride resin (B) before drying".

The mode of the polyvinyl chloride resin (B) is 0.10 μm to 0.50 μm, preferably 0.11 μm to 0.48 μm, and more preferably 0.12 μm to 0.46 μm. It is more preferably 0.13 μm to 0.44 μm, more preferably 0.14 μm to 0.42 μm, more preferably 0.15 μm to 0.40 μm, and 0.16 μm to 0.39 μm. It is more preferably 0.17 μm to 0.38 μm, and particularly preferably 0.18 μm to 0.37 μm. According to this configuration, the curable composition has the advantages of better initial fixation and better storage stability.

In particular, when the mode of the polyvinyl chloride resin (B) is 0.50 μm or less, the curable composition has an advantage of being excellent in storage stability. This is inferred as follows, but one embodiment of the present invention is not limited to the following inference:
As the frequency of the polyvinyl chloride resin (B) increases, the aggregation of the polyvinyl chloride resin (B) is loosened during storage of the curable composition, and the loosened polyvinyl chloride resin (B) has a curable composition. Disperses evenly in the object. As a result, it is presumed that the larger the mode of the polyvinyl chloride resin (B), the greater the effect of increasing the viscosity of the curable composition by hydrogen bonding. In other words, it is presumed that as the mode of the polyvinyl chloride resin (B) increases, the viscosity of the curable composition after storage tends to increase. On the other hand, as the mode of the polyvinyl chloride resin (B) becomes smaller, the polyvinyl chloride resin (B) is already contained in the curable composition in a form close to the primary particles in the state before storage of the curable composition. Spread. As a result, it is presumed that the change in viscosity of the curable composition is small before and after storage of the curable composition.

The method for producing the polyvinyl chloride resin (B) is not particularly limited. As a method for producing the polyvinyl chloride resin (B), a polymerization method such as an emulsion polymerization method or a fine suspension polymerization method is preferably used, and among them, the primary particle size of the polyvinyl chloride resin (B) is controlled to be small. The emulsification polymerization method is more preferably used because it is easy to carry out. Further, the polyvinyl chloride resin (B) can be obtained by drying the latex obtained after the polymerization of the polyvinyl chloride resin by a spray drying method, a fluidized bed drying method or the like.

The content of the polyvinyl chloride resin (B) in the present curable composition is 10 parts by weight to 500 parts by weight and 20 parts by weight to 450 parts by weight with respect to 100 parts by weight of the organic polymer (A). It is preferably 30 parts by weight to 400 parts by weight, more preferably 40 parts by weight to 350 parts by weight, more preferably 50 parts by weight to 300 parts by weight, and 60 parts by weight to 60 parts by weight. It is more preferably 250 parts by weight, and particularly preferably 70 parts by weight to 200 parts by weight. According to this composition, the curable composition has the advantage of being better at initial immobilization.

[2-3. Calcium carbonate (C)]
Calcium carbonate (C) can function as a filler in the curable composition. Examples of the filler include known general-purpose fillers such as kaolin, aluminum hydroxide, aluminum oxide, fume silica, silica powder, glass filler, carbon black, hollow filler, and barium sulfate. Compared to a curable composition that does not contain calcium carbonate (C) as a filler and contains other general purpose fillers, this curable composition that contains calcium carbonate (C) as a filler is flexible and / or various adherends. It has the advantage of excellent adhesion to calcium. In addition to calcium carbonate (C), the present curable composition may further contain the above-mentioned general-purpose filler other than calcium carbonate (C).

There are no particular restrictions on calcium carbonate (C). For example, (a) calcium carbonate, which is produced by introducing CO ₂ gas into an aqueous slurry of Ca (OH) ₂ , and (b) limestone are mechanically crushed and classified. The heavy calcium carbonate thus obtained, and (c) colloidal calcium carbonate (sometimes referred to as precipitated calcium carbonate), and the like can be mentioned. In general, collagen carbonate and colloidal calcium carbonate have a smaller volume average particle size than heavy calcium carbonate.

The BET specific surface area of calcium carbonate (C) is preferably 1 m ² / g to 100 m ² / g, more preferably 2 m ² / g to 80 m ² / g, and 5 m ² / g to 50 m ² / g. It is more preferably g. When the BET specific surface area of calcium carbonate (C) is 1 m ² / g or more, the thixotropic property of the curable composition becomes good. When the BET specific surface area of calcium carbonate (C) is 100 m ² / g or less, aggregation of calcium carbonate (C) with each other is restricted in the curable composition, and calcium carbonate (C) in the curable composition is restricted. Good dispersibility. As a result, when the BET specific surface area of calcium carbonate (C) is 100 m ² / g or less, the curable composition has good thixotropic properties. In the present specification, the BET specific surface area of calcium carbonate (C) is a value measured using a specific surface area measuring device (Macsorb HM model-1208 manufactured by Mountech Co., Ltd. or Flowsorb II2300 manufactured by Micromeritic Co., Ltd.).

Calcium carbonate (C) may be calcium carbonate surface-treated with a surface treatment agent. The surface treatment agent is not particularly limited, and for example, a fatty acid-based compound is preferably used. The fatty acid-based compound is not particularly limited, and for example, one or more selected from the group consisting of fatty acids, fatty acid salts, fatty acid derivatives, and fatty acid derivative salts can be preferably mentioned.

The fatty acid is not particularly limited, but saturated fatty acid, unsaturated fatty acid, alicyclic carboxylic acid and the like can be preferably used. Specifically, caproic acid, capric acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, alignment acid, behenic acid, lignoseric acid, cellotic acid, montanic acid, melicic acid, Lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, obscilic acid, carroleaic acid, undecylenic acid, linderic acid, tsuzuic acid, fizeteric acid, moristrenic acid, palmitreic acid, petroseric acid, oleic acid, ellaic acid , Asclebic acid, vacene acid, gadrain acid, gondoic acid, setreic acid, erucic acid, brushzic acid, seracholeic acid, ximenic acid, lumecic acid, sorbic acid, linoleic acid, stearyl stearate, lauryl stearate, stearyl palmitate, Examples include lauryl palmitate. These can be used alone or in combination of two or more. Of the fatty acids, palmitic acid, stearic acid, and oleic acid are particularly preferable.

The method for producing the surface-treated calcium carbonate (C) is not particularly limited, and the above-mentioned calcium carbonate is surface-treated (coated) with the above-mentioned fatty acid compound, and then dehydrated and dried according to a conventional method. Examples thereof include a method of pulverizing through a step such as crushing.

The content of calcium carbonate (C) in the present curable composition is 150 parts by weight to 500 parts by weight, and more than 150 parts by weight and 500 parts by weight or less with respect to 100 parts by weight of the organic polymer (A). It is preferably 160 parts by weight to 500 parts by weight, more preferably 170 parts by weight to 500 parts by weight, more preferably 180 parts by weight to 500 parts by weight, and more preferably 190 parts by weight to 500 parts by weight. It is more preferably 500 parts by weight, particularly preferably 200 parts by weight to 500 parts by weight, and most preferably 250 parts by weight to 500 parts by weight. According to this composition, the curable composition has the advantage of being better at initial immobilization. Further, by setting the content of calcium carbonate (C) to 150 parts by weight or more, a curable composition having excellent initial fixing property despite a small content of the organic polymer (A) (for example, 25% by weight or less). Things are possible. As a result, there is an advantage that a curable composition having excellent initial fixing property and being inexpensive can be provided. From the viewpoint of initial fixing property and production cost of the curable composition, the content of calcium carbonate (C) in the present curable composition is 170 parts by weight to 450 parts by weight with respect to 100 parts by weight of the organic polymer (A). It may be 180 parts by weight to 400 parts by weight, 190 parts by weight to 350 parts by weight, or 200 parts by weight to 300 parts by weight.

In this curable composition, it is preferable to use as calcium carbonate (C) in combination of two or more kinds of calcium carbonate having different volume average particle diameters. The present curable composition may be, as calcium carbonate (C), for example, (a) calcium carbonate (C1) having a volume average particle size of 0.01 μm or more and less than 0.50 μm (for example, glued calcium carbonate or colloidal calcium carbonate). And (b) calcium carbonate (C2) having a volume average particle size of 0.50 μm to 10.00 μm (for example, heavy calcium carbonate without surface treatment) are preferably contained.

The present curable composition is based on 100 parts by weight of the organic polymer (A).
(I) (a) Calcium carbonate (C1) with a volume average particle diameter of 0.01 μm or more and less than 0.50 μm 0 parts by weight to 300 parts by weight, and (b) a volume average particle diameter of 0.50 μm to 10.00 μm. It is preferable to contain 0 part by volume to 500 parts by volume of calcium carbonate (C2).
(Ii) (a) Calcium carbonate (C1) with a volume average particle diameter of 0.03 μm to 0.40 μm 0 parts by weight to 250 parts by weight, and (b) a volume average particle diameter of 0.50 μm to 10.00 μm. It is more preferable to contain a certain calcium carbonate (C2) of 100 parts by volume to 500 parts by volume.
(Iii) (a) Calcium carbonate (C1) with a volume average particle diameter of 0.05 μm to 0.20 μm 0 parts by weight to 200 parts by weight, and (b) a volume average particle diameter of 0.60 μm to 9.00 μm. It is more preferable to contain a certain calcium carbonate (C2) of 150 parts by volume to 500 parts by volume.
(Iv) (a) Calcium carbonate (C1) with a volume average particle diameter of 0.05 μm to 0.15 μm 0 parts by weight to 150 parts by weight, and (b) a volume average particle diameter of 0.70 μm to 5.00 μm. It is particularly preferable to contain a certain calcium carbonate (C2) of 150 parts by volume to 500 parts by volume.
According to this structure, the curable composition has the advantages of (a) being superior in initial fixing property and (b) being excellent in handleability because it is easily discharged from the storage container. In the present specification, the volume average particle size of calcium carbonate (C) is a value obtained by measuring by a laser light diffraction / scattering method. Further, "volume average particle size" is synonymous with "d50 particle size".

The ratio of the weight of calcium carbonate (C1) to the weight of calcium carbonate (C2) in calcium carbonate (C) (weight of calcium carbonate (C1) / weight of calcium carbonate (C2)) is not particularly limited, but is not particularly limited, for example. It is preferably 1.0 or less, more preferably 0.9 or less, further preferably 0.8 or less, and particularly preferably 0.7 or less.

The ratio ((B) / (C)) of the content of the polyvinyl chloride resin (B) to the content of calcium carbonate (C) in the present curable composition is 0.2 to 0.8. It is preferably 0.2 to 0.7, more preferably 0.2 to 0.6, and particularly preferably 0.2 to 0.5. According to this configuration, (a) the curable composition does not impair the ejection property, (b) the curable composition has a low specific density, and (c) the heat resistance and / or weather resistance of the cured product is impaired. It has advantages such as never. That is, when (B) / (C) is within the above-mentioned range, the curable composition has an advantage of exhibiting good high-tack adhesiveness. Further, the fact that the curable composition has a low specific density means that even a curable composition having the same volume is lighter. Compared with the curable composition having a high specific density, the curable composition having a low specific density has an advantage that the production cost is low and the transportation and storage costs are also low.

[2-4. Dehydrating agent (D)]
The present curable composition may further contain a dehydrating agent (D) in addition to the organic polymer (A), the polyvinyl chloride resin (B) and calcium carbonate (C). When the present curable composition contains the dehydrating agent (D), the curable composition has an advantage of being excellent in storage stability.

The dehydrating agent (D) is not particularly limited, but is preferably a substance that absorbs water and / or moisture. Examples of the dehydrating agent (D) include vinylsilane compound, silicate compound, calcium oxide, zeolite compound and methyl orthoate. Among these, as the dehydrating agent (D), a vinylsilane compound and a silicate compound are preferable, and a vinylsilane compound is more preferable. According to this composition, the curable composition has the advantage of being superior in storage stability.

Examples of the vinylsilane compound that can be used as the dehydrating agent (D) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldipropoxysilane, and vinyldimethyl. Methoxysilane, vinyldimethylethoxysilane, vinyldimethylpropoxysilane, vinylethyldimethoxysilane, vinylethyldiethoxysilane, vinylethyldipropoxysilane, vinyldiethylmethoxysilane, vinyldiethylethoxysilane, vinyldiethylpropoxysilane, vinylpropyldimethoxysilane, Examples include vinylpropyldiethoxysilane, vinylpropyldipropoxysilane, vinyldipropylmethoxysilane, vinyldipropylethoxysilane, vinyldipropylpropoxysilane, methylsilicate, methylsilicate condensate, ethylsilicate and ethylsilicate condensate. Be done. Among these, as the vinylsilane compound that can be used as the dehydrating agent (D), a condensate of vinyltrimethoxysilane and ethyl silicate is preferable, and vinyltrimethoxysilane is more preferable. According to this composition, the curable composition has the advantage of being more excellent in storage stability.

The content of the dehydrating agent (D) in the present curable composition is not particularly limited. The content of the dehydrating agent (D) in the present curable composition is preferably 2 parts by weight to 10 parts by weight, preferably 3 parts by weight to 8 parts by weight, based on 100 parts by weight of the organic polymer (A). It is more preferably 4 parts by weight to 6 parts by weight. According to this composition, the curable composition has the advantage of being superior in storage stability.

The amount of water (water content) in the present curable composition is not particularly limited, but it is preferable that the amount is smaller because it is more excellent in storage stability. The amount of water (moisture content) in the present curable composition is preferably 200 ppm to 10000 ppm, more preferably 500 ppm to 8000 ppm, and more preferably 1000 ppm to 7000 ppm in 100 parts by weight of the curable composition. It is more preferably 1500 ppm to 6000 ppm, and particularly preferably 1500 ppm to 6000 ppm.

[2-5. Other ingredients]
The present curable composition may contain other components in addition to the above-mentioned components, if necessary. Other components include, but are not limited to, the following substances, for example: plasticizer; anti-dripping agent (sometimes referred to as thixotropic agent); adhesive-imparting agent; antioxidant. Photocurable substances; Hollow fillers; Light stabilizers; Solvents and / or diluents; UV absorbers; Flame retardants; Curability modifiers; Lubricants; Colorants; Foaming agents; Antifungal materials.

Examples of the plasticizer include epoxy compounds, phthalate compounds, and polyether compounds. Examples of the epoxy-based compound include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Examples of phthalate ester compounds include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dinormal hexyl phthalate, bis (2-ethylhexyl) phthalate, dinormal octyl phthalate, diisononyl phthalate, and phthalate. Examples thereof include dinonyl acid, diisodecyl phthalate, diisoundecyl phthalate, and bisbutylbenzyl phthalate. Examples of the polyether compound include polyoxypropylene diol, polyethylene glycol, polyoxybutylene glycol, and a copolymer of ethylene oxide and propylene oxide. One of these plasticizers may be used alone, or two or more thereof may be used in combination. When the present curable composition contains a plasticizer, the curable composition has an advantage of being excellent in adhesiveness to various adherends.

Examples of the anti-dripping agent include polyamide waxes; hydrogenated castor oil and hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate; and the like. One of these anti-dripping agents may be used alone, or two or more thereof may be used in combination. When the present curable composition contains an anti-dripping agent, it has an advantage that sagging is prevented during construction of the curable composition, that is, an advantage that the workability of the curable composition is improved.

Examples of the adhesive-imparting agent include aminosilane-based compounds, epoxysilane-based compounds, isocyanatesilane-based compounds, and acrylicsilane-based compounds. As the adhesiveness-imparting agent, an aminosilane compound is preferable, and 3- (2-aminoethylamino) propyltrimethoxysilane is particularly preferable. One of these adhesive-imparting agents may be used alone, or two or more thereof may be used in combination. When the present curable composition contains an adhesive-imparting agent, the curable composition has an advantage that the adhesiveness to the adherend is improved and the strength of the cured product is also increased.

Examples of the antioxidant include hindered phenol compounds, monophenol compounds, polyphenol compounds and the like. As the antioxidant, a hindered phenolic compound is particularly preferable. These antioxidants may be used alone or in combination of two or more. When the present curable composition contains an antioxidant, (a) the advantage that the deterioration of the curable composition can be delayed even when the curable composition is stored for a long period of time, and (b) the curable composition can be used. It has the advantage that the performance of the curable composition can be maintained even when stored under high temperature conditions.

Examples of the curing catalyst include organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, and alkoxy metals.

Specific examples of the organic tin compound include dibutyl tin dilaurate, dibutyl tin dioctanoate, dibutyl tin bis (butyl maleate), dibutyl tin diacetate, dibutyl tin oxide, dibutyl tin bis (acetylacetonate), and dioctyl tin bis (acetylacetate). Nart), dioctyl tin dilaurate, dioctyl tin distearate, dioctyl tin diacetate, dioctyl tin oxide, reaction product of dibutyl tin oxide and silicate compound, reaction product of dioctyl tin oxide and silicate compound, dibutyl tin oxide and phthalate ester. Examples include the reactants of.

Specific examples of the metal carboxylate salt include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, and the like. As the carboxylic acid metal salt, a salt obtained by appropriately combining the following carboxylic acid and various metals can also be used.

Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine, etc .; pyridine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1, Nitrogen-containing heterocyclic compounds such as 5-diazabicyclo [4,3,0] nonen-5 (DBN); guanidines such as guanidine, phenylguanidine, diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide and 1- Viguanides such as phenylbiguanide; amino group-containing silane coupling agents; ketimine compounds, and the like can be mentioned.

Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

Specific examples of the alkoxy metal include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate) and diisopropoxytitanium bis (ethylacetatete); aluminum tris (acetylacetonate), diisopropoxyaluminum ethylacetoacetate and the like. Aluminum compounds; zirconium compounds such as zirconium tetrakis (acetylacetonate), and the like.

As other curing catalysts (also referred to as silanol condensation catalysts), fluorine anion-containing compounds, photoacid generators and photobase generators can also be used.

Further, in order to increase the activity of the curing catalyst, an amine compound may be used in combination with the curing catalyst. Examples of such amine compounds include known amine compounds such as octylamine, decylamine, laurylamine, oleylamine, and di-n-octylamine.

Examples of the colorant include pigments such as tin oxide, carbon black, titanium oxide, and red iron oxide.

[2-6. Initial fixation]
The present curable composition is excellent in initial fixing property. The method for measuring the initial fixability of the curable composition will be described in detail in Examples.

The larger the initial fixing property of the present curable composition is, the more preferable it is, for example, it is preferably larger than 100 g, more preferably 150 g or more, more preferably 200 g or more, and even more preferably 250 g or more. , 300 g or more, more preferably 350 g or more, more preferably 400 g or more, further preferably 450 g or more, and particularly preferably 500 g or more. According to this structure, the curable composition has an advantage that it can be more preferably used by a high-tack adhesive.

[2-7. Production method]
The method for producing the present curable composition is not particularly limited. The present curable composition is produced (prepared) by mixing an organic polymer (A), a polyvinyl chloride resin (B) and calcium carbonate (C), and optionally a dehydrating agent (D) and other components. can. The order in which the organic polymer (A), the polyvinyl chloride resin (B) and the calcium carbonate (C), and optionally the dehydrating agent (D) and other components are mixed is not particularly limited. Each component may be mixed one by one, or a plurality of components may be mixed at the same time. The mixing device used for producing the curable composition is not particularly limited, and a known mixing device such as a three-roll mill can be used.

The curable composition does not need to be completely sealed and stored. When the present curable composition is stored for a long period of time, it is preferable to store the curable composition in a closed container such as a cartridge. The cartridge is not particularly limited, and examples thereof include an aluminum cartridge.

[3. Hardened product]
A cured product can be obtained by curing the present curable composition. A cured product obtained by curing the present curable composition is also an embodiment of the present invention. The cured product according to the embodiment of the present invention is described in the above [2. Curable composition] is a cured product obtained by curing the curable composition described in the section. For example, by exposing the present curable composition to air at room temperature, the curable composition is cured by reacting with moisture in the air, and a cured product according to an embodiment of the present invention can be obtained. ..

[4. Use]
The present curable composition can be suitably used as a composition for an adhesive, for example, as a one-component adhesive. Since the present curable composition is excellent in initial fixing property, it can be particularly preferably used as a high-tack adhesive. Therefore, the curable composition and the adhesive according to one embodiment of the present invention, which will be described later, are used for vehicle bodies / parts of automobiles, body / parts of large vehicles such as trucks and buses, vehicle / parts of trains, and parts for aircraft. It can be particularly preferably used in the field of building materials such as marine parts, containers, electric / electronic parts, home appliances, various mechanical parts, mirrors, various decorative board panels, and sashes.

[5. glue〕
The adhesive according to one embodiment of the present invention is described in [2. Curable Composition] includes the curable composition described in the section. Since the adhesive according to the embodiment of the present invention has the above-mentioned structure, it is excellent in initial fixing property. Therefore, the adhesive according to one embodiment of the present invention can be particularly preferably used as (a) a one-component adhesive and / or (b) a high-tack adhesive. The curable composition itself can be used as an adhesive according to an embodiment of the present invention.

One embodiment of the present invention may have the following configuration.

[1] Contains 100 parts by weight of an organic polymer (A) having a hydrolyzable silicon group, 10 parts by weight to 500 parts by weight of a polyvinyl chloride resin (B), and 150 parts by weight to 500 parts by weight of calcium carbonate (C). , A curable composition having a maximum frequency of the polyvinyl chloride resin (B) of 0.10 μm to 0.50 μm.

[2] The curable composition according to [1], which further contains 2 parts by weight to 10 parts by weight of the dehydrating agent (D).

[3] The ratio ((B) / (C)) of the content of the polyvinyl chloride resin (B) to the content of the calcium carbonate (C) is 0.2 to 0.8, [1]. Alternatively, the curable composition according to [2].

[4] The organic polymer (A) is any one of [1] to [3], which is a mixture of a linear organic polymer (A1) and a branched organic polymer (A2). The curable composition according to.

[5] The content of the calcium carbonate (C) is 250 parts by weight to 500 parts by weight with respect to 100 parts by weight of the organic polymer (A), in any one of [1] to [4]. The curable composition according to description.

[6] The calcium carbonate (C) includes calcium carbonate (C1) having a volume average particle size of 0.05 μm to 0.15 μm and calcium carbonate (C2) having a volume average particle size of 0.70 μm to 5.00 μm. ), And the ratio of the weight of the calcium carbonate (C1) to the weight of the calcium carbonate (C2) (weight of the calcium carbonate (C1) / weight of the calcium carbonate (C2)) is 1.0 or less. The curable composition according to any one of [1] to [5].

[7] A cured product obtained by curing the curable composition according to any one of [1] to [6].

[8] An adhesive containing the curable composition according to any one of [1] to [6].

Hereinafter, one embodiment of the present invention will be described in more detail with reference to specific examples. The present invention is not limited to the following examples.

<Material>
The materials used in each example and comparative example are as follows.

(Organic polymer (A))
-Organic polymer A1; Organic polymer obtained in Synthesis Example 1 described later-Organic polymer A2; Organic polymer obtained in Synthesis Example 2 described later (polyvinyl chloride resin (B))
-Polyvinyl chloride resin (B1); polyvinyl chloride resin / polyvinyl chloride resin (B2) obtained in Synthetic Example 3 described later; polyvinyl chloride resin / polyvinyl chloride resin (B3) obtained in Synthetic Example 4 described later. The polyvinyl chloride resin (calcium carbonate (C)) obtained in Synthesis Example 5 described later.
-Calcium carbonate (C1); Neolite SP (Made by Takehara Chemical Industry, colloidal calcium carbonate (volume average particle size 0.08 μm))
-Calcium carbonate (C2); Omya 1T (manufactured by Omyacarb, heavy calcium carbonate (d50 particle size 2.00 μm))
(Dehydrating agent (D))
-A-171; Momentive, vinyltrimethoxysilane (plasticizer)
-Polyoxypropylene diol (molecular weight about 3000)
(Anti-sagging agent)
・ Disparon 308; Kusumoto Kasei, hydrogenated castor oil derivatives (antioxidant)
-Irganox 1010: BASF's hindered phenolic antioxidant-Nocrack NS-6: Ouchi Shinko Kagaku Kogyo's hindered phenolic antioxidant (adhesive-imparting agent)
A-1120: Momentive, 3- (2-aminoethylamino) propyltrimethoxysilane (curing catalyst)
U303; Nitto Kasei, dibutyl tin compound ・ MSCAT02; Nihon Kagaku Sangyo, dibutyl tin compound (colorant)
・ R820; Titanium oxide manufactured by Ishihara Sangyo <Evaluation method>
Each evaluation method in Examples and Comparative Examples will be described below.

(Initial fixation)
The initial fixability of the curable compositions obtained in Examples and Comparative Examples was measured by performing the following (1) to (4) in order.
(1) A curable composition having a thickness of 3 mm was applied to one surface of the aluminum plate A;
(2) The aluminum plate A was fixed so that the plate surface was parallel to the vertical direction;
(3) Curability of another aluminum plate B having a length of 100 mm, a width of 25 mm, and a thickness of 3 mm is applied to the aluminum plate A so that the plate surface of the aluminum plate B and the plate surface of the aluminum plate A are parallel to each other. It was brought into close contact with the aluminum plate A via the composition (that is, a laminate in which the aluminum plate B-curable composition-aluminum plate A was laminated in this order in the horizontal direction was obtained). At this time, (a) the aluminum plate B and the aluminum plate A are brought into close contact with each other by manually pressing the aluminum plate B against the curable composition of the aluminum plate A, and (b) the length of the aluminum plate B is 100 mm. Of these, the lower 75 mm was in close contact with the aluminum plate A, and the upper 25 mm was not in close contact with the aluminum plate A;
(4) Within 5 seconds after the aluminum plate B was brought into close contact with the aluminum plate A, only the springs were installed 25 mm above the aluminum plate B which was not in close contact with the aluminum plate A, and only the springs were pulled up.
The maximum stress (g) exhibited by the spring scale was taken as the initial fixing property.

(Evaluation method of storage stability)
For the curable compositions obtained in Examples and Comparative Examples, immediately after the curable composition was prepared (specifically, within 7 days after the preparation), the condition of 2 rpm using the B-type viscosity was used. The viscosity of the curable composition was measured and used as the initial viscosity (mPa · s). The curable composition was filled in a 330 ml paper aluminum cartridge. Cartridges filled with the curable composition were stored in a dryer set at 50 ° C. for 4 weeks.
The viscosity of the curable composition after storage was measured using the B-type viscosity under the condition of 2 rpm, and the viscosity after storage (mPa · s) was obtained. The viscosity change (%) was calculated by the following formula.
Viscosity change (%) = Viscosity after storage (mPa · s) / Initial viscosity (mPa · s) × 100.
When the viscosity change was less than 200%, it was evaluated as excellent in storage stability, and when the viscosity change was 200% or more, it was evaluated as inferior in storage stability.
The curable compositions obtained in Examples and Comparative Examples are stored in a closed plastic container after preparation in each Example and Comparative Example until the storage stability is evaluated. Was done.

(Measuring method of dumbbell physical properties)
The curable composition was packed in a 3 mm thick sheet-like formwork at 23 ° C. and 50% relative humidity. The curable composition in the sheet-shaped mold was cured at 23 ° C. and 50% relative humidity for 3 days, and then the obtained cured product was cured in a 50 ° C. dryer for 4 days to obtain a sheet-shaped cured product. rice field.
The obtained cured product was punched into a No. 3 dumbbell mold according to JIS K 6251 to obtain a test piece. Using the obtained test piece, a tensile test (tensile speed 200 mm / min) was performed using an autograph at 23 ° C. and 50% relative humidity, and 100% elongation modulus, stress at break (tensile strength TB), and The elongation at break (EB) was measured.

(Shear strength)
As the adherend, two sheets of SUS304 degreased with acetone were used. The curable composition was applied onto a single adherend at 23 ° C. and 50% relative humidity with a coating area of 25 mm × 25 mm and a thickness of 50 μm. Immediately after that, another adherend was attached (adhered) to the adherend coated with the curable composition via the curable composition. The adherend was allowed to stand at 85 ° C. and 85% relative humidity for 3 days to cure the curable composition between the adherends. The obtained adherend was subjected to a tensile shear test (tensile speed 50 mm / min) using an autograph, and the stress at break (TB) was measured.

(Synthesis Example 1)
(Preparation of organic polymer (A1))
Propylene oxide was polymerized in the presence of a zinc hexacyanocovalent glyme complex catalyst using polyoxypropylene glycol having a number average molecular weight of about 4500 as an initiator. By such polymerization, polyoxypropylene (P-1) having a number average molecular weight of 25500 and a molecular weight distribution of Mw / Mn = 1.26 having a hydroxyl group at the terminal was obtained. Next, a methanol solution containing sodium methoxide at a concentration of 28% (w / w) was added to the obtained reaction solution containing polyoxypropylene (P-1). Here, the methanol solution of sodium methoxide is added to the reaction solution so as to have 1.2 molar equivalents of sodium methoxide with respect to 1 molar equivalent of the hydroxyl group at the terminal of the obtained polyoxypropylene (P-1). bottom. Methanol was distilled off from the obtained reaction solution by vacuum devolatile. Then, allyl chloride is added to the reaction solution so that the amount of allyl chloride is 1.5 molar equivalents with respect to 1 molar equivalent of the hydroxyl group at the terminal of polyoxypropylene (P-1) to obtain the hydroxyl group at the terminal. Converted to an allyl group. Subsequently, unreacted allyl chloride was removed from the reaction solution by vacuum volatilization to obtain unpurified polyoxypropylene. The obtained unpurified polyoxypropylene was mixed and stirred with n-hexane and water, and then water was removed from the mixed solution obtained by centrifugation to obtain a hexane solution. The metal salt in polyoxypropylene was removed by devolatile hexane from the obtained hexane solution under reduced pressure. By the above operation, polyoxypropylene (Q-1) having an allyl group at the terminal was obtained. A platinum divinyldisiloxane complex solution was added to polyoxypropylene (Q-1) so as to be 50 μl of a platinum divinyldisiloxane complex solution (3 wt% isopropanol solution in terms of platinum) with respect to 500 g of polyoxypropylene. While stirring the obtained mixture, 4.5 g of dimethoxymethylsilane was slowly added dropwise to the mixture. After reacting the obtained mixed solution at 100 ° C. for 2 hours, unreacted dimethoxymethylsilane is distilled off under reduced pressure to obtain polyoxypropylene having a dimethoxymethylsilyl group at the terminal, which is a linear chain. An organic polymer (A1) in the form of a state was obtained. It was found that the number average molecular weight of the organic polymer (A1) was 25,500, and the organic polymer (A1) had an average of 0.7 dimethoxymethylsilyl groups at one terminal and an average of 1.4 in one molecule. rice field.

(Synthesis Example 2)
(Preparation of organic polymer (A2))
Polyoxypropylene triol having a number average molecular weight of about 4500 was used as an initiator, and propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate grime complex catalyst. By such polymerization, polyoxypropylene (P-2) having a number average molecular weight of 16400 and a molecular weight distribution of Mw / Mn = 1.31 having a hydroxyl group at the terminal was obtained. Next, a methanol solution containing sodium methoxide at a concentration of 28% (w / w) was added to the obtained reaction solution containing polyoxypropylene (P-2). Here, the methanol solution of sodium methoxide is added to the reaction solution so as to have 1.2 molar equivalents of sodium methoxide with respect to 1 molar equivalent of the hydroxyl group at the terminal of the obtained polyoxypropylene (P-2). bottom. Methanol was distilled off from the obtained reaction solution by vacuum devolatile. Then, allyl chloride is added to the reaction solution so that the amount of allyl chloride is 1.5 molar equivalents with respect to 1 molar equivalent of the hydroxyl group at the terminal of polyoxypropylene (P-2) to obtain the hydroxyl group at the terminal. Converted to an allyl group. Subsequently, unreacted allyl chloride was removed from the reaction solution by vacuum volatilization to obtain unpurified polyoxypropylene. The obtained unpurified polyoxypropylene was mixed and stirred with n-hexane and water, and then water was removed from the mixed solution obtained by centrifugation to obtain a hexane solution. The metal salt in polyoxypropylene was removed by devolatile hexane from the obtained hexane solution under reduced pressure. By the above operation, polyoxypropylene (Q-2) having an allyl group at the terminal was obtained. A platinum divinyldisiloxane complex solution was added to polyoxypropylene (Q-1) so as to be 50 μl of a platinum divinyldisiloxane complex solution (3 wt% isopropanol solution in terms of platinum) with respect to 500 g of polyoxypropylene. While stirring the obtained mixture, 8.9 g of dimethoxymethylsilane was slowly added dropwise to the mixture. After reacting the obtained mixed solution at 100 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene having a dimethoxymethylsilyl group at the terminal, which was branched. Organic polymer (A2) was obtained. It was found that the number average molecular weight of the organic polymer (A2) was 16400, and the organic polymer (A2) had an average of 0.7 dimethoxymethylsilyl groups at one terminal and an average of 2.1 in one molecule. rice field.

(Synthesis Example 3)
(Preparation of polyvinyl chloride resin (B-1))
In a pressure-resistant container with a 300L stainless steel stirrer with a jacket that has been degassed in advance, 100 kg of vinyl chloride monomer, 100 kg of ion-exchanged water, 175 g of myristic acid, 1.3 L of 28% (w / w) aqueous ammonia solution, sodium- 85 g of formaldehyde-sulfoxylate (manufactured by Longarit), 1.5 g of ferrous sulfate and 2.5 g of ethylenediaminetetraacetic acid-2-sodium were charged. Then, the temperature of the mixed solution was raised to 47.6 ° C., and tert-butyl hydroperoxide adjusted to 0.3% (w / w) in advance was continuously added to the mixed solution for polymerization. Here, 7.8 kg of a 10.8 wt% ammonium myristate aqueous solution is continuously added to the mixed solution from the time when the conversion rate from the monomer to the polymer reaches 5% to the time when it reaches 70%. As a result, the polymerization was carried out until the polymerization pressure was 0.15 MPa lower than the initial pressure (0.62 MPa). Then, the monomer remaining in the mixed solution was recovered from the mixed solution to obtain a latex containing a vinyl chloride resin. The mode of the vinyl chloride resin in the obtained latex was 0.18 μm. The obtained latex was passed through a sieve having a mesh size of 100 mesh to remove coarse particles, and then the passed solution was spray-dried to obtain a polyvinyl chloride resin (B-1).

(Synthesis Example 4)
(Preparation of polyvinyl chloride resin (B-2))
A latex containing a vinyl chloride resin was obtained by the same operation as in Production Example 1 except that the amount of myristic acid charged in the pressure-resistant container was changed to 70 g. The mode of the vinyl chloride resin in the obtained latex was 0.37 μm. The obtained latex was passed through a sieve having a mesh size of 100 mesh to remove coarse particles, and then the passed solution was spray-dried to obtain a polyvinyl chloride resin (B-2).

(Synthesis Example 5)
(Adjustment of polyvinyl chloride resin (B-3))
A 300 L stainless steel stirrer-equipped pressure vessel with a jacket was charged with 100 kg of ion-exchanged water, 790 g of linear sodium dodecylbenzene sulfonate, 270 g of stearyl alcohol, 270 g of stearic acid, and 60 g of t-butylperoxyneododecanoate. After that, the pressure-resistant container was degassed. Next, 100 kg of vinyl chloride monomer was added into the pressure-resistant container, and the mixed solution in the pressure-resistant container was homogenized and homogenized for 30 minutes. Then, the temperature of the mixed solution was raised to 44.5 ° C. to start polymerization. Polymerization was carried out until the polymerization pressure was 0.05 MPa lower than the initial pressure. Then, the monomer remaining in the mixed solution was recovered from the mixed solution to obtain a latex containing a vinyl chloride resin. The mode of the vinyl chloride resin in the obtained latex was 1.0 μm. The obtained latex was passed through a sieve having a mesh size of 100 mesh to remove coarse particles, and then the passed solution was spray-dried to obtain a polyvinyl chloride resin (B-3).

(Examples 1 to 3 and Comparative Examples 1 to 2)
A curable composition was prepared as follows. First, among the components shown in Table 1, each component excluding the dehydrating agent (D), the anti-dripping agent, the adhesive-imparting agent, and the curing catalyst is weighed by weight as shown in Table 1, and the weighed components are put into a 3-roll mill. The mixture was subjected to a uniform dispersed paste. Then, the dispersed paste was dehydrated under reduced pressure conditions at 120 ° C. for 2 hours. After confirming that the water content of the dispersed paste reached 500 ppm or less, the dispersed paste was cooled until the temperature of the dispersed paste became 50 ° C. or less. Then, the remaining components were added to the dispersed paste, and the obtained mixture was subjected to stirring and defoaming operations to obtain a curable composition. The obtained curable composition was filled in an aluminum cartridge. The obtained curable composition was evaluated for initial immobility and storage stability by the method described above. The results of initial fixation are shown in Table 1. The curable composition obtained in Examples 1 to 3 is a curable composition according to an embodiment of the present invention, and is also an adhesive according to an embodiment of the present invention.

Regarding storage stability, the curable compositions of Examples 1 to 3 and Comparative Example 1 had a viscosity change of less than 200% and were excellent in storage stability. On the other hand, the curable composition of Comparative Example 2 had a viscosity change of 200% or more and was inferior in storage stability.

As shown in Table 1, an example containing a specific amount of the organic polymer (A), a polyvinyl chloride resin (B) having a maximum frequency of 0.1 μm to 0.5 μm, and calcium carbonate (C), respectively. It was found that the curable compositions 1 to 3 were excellent in initial fixing property. Further, in Example 2 in which the ratio ((B) / (C)) of the content of the polyvinyl chloride resin (B) to the content of calcium carbonate (C) is 0.8 or less, (B) / ( It was found that the initial fixability was superior to that of Example 3 in which C) was 1.1. On the other hand, it was found that the curable compositions of Comparative Examples 1 and 2 containing the polyvinyl chloride resin (B) having a mode diameter of 1.0 μm were inferior in initial fixing property.

Since the curable composition of Comparative Example 2 is inferior in storage stability, it is not suitable for (a) an adhesive application such as transportation and long-term storage in a store after the curable composition is produced. it is conceivable that.

(Examples 4 to 8)
A curable composition was prepared as follows. First, among the components shown in Table 2, each component excluding the dehydrating agent (D), the anti-dripping agent, the adhesive-imparting agent, and the curing catalyst is weighed by weight as shown in Table 2, and the weighed components are put into a 3-roll mill. The mixture was subjected to a uniform dispersed paste. Then, the dispersed paste was dehydrated under reduced pressure conditions at 120 ° C. for 2 hours. After confirming that the water content of the dispersed paste reached 500 ppm or less, the dispersed paste was cooled until the temperature of the dispersed paste became 50 ° C. or less. Then, the remaining components were added to the dispersed paste, and the obtained mixture was subjected to stirring and defoaming operations to obtain a curable composition. The obtained curable composition was filled in an aluminum cartridge. The obtained curable composition was evaluated for initial immobility and storage stability by the method described above. In addition, the dumbbell physical properties and shear strength of the cured product of the curable composition were evaluated by the above-mentioned method. The results of initial fixation, dumbbell physical properties and shear strength are shown in Table 1. The curable compositions obtained in Examples 4 to 8 are curable compositions according to an embodiment of the present invention, and are also adhesives according to an embodiment of the present invention.

Regarding storage stability, the curable compositions of Examples 4 to 8 had a viscosity change of less than 200% and were excellent in storage stability.

As shown in Table 2, it was found that the curable compositions of Examples 4 to 8 were also excellent in initial fixing property as in Examples 1 to 3. Here, the curable compositions of Examples 4, 7 and 8 are a mixture of the organic polymer (A1) in which the organic polymer (A) is linear and the organic polymer (A2) in which the organic polymer (A) is branched. In the curable composition of Example 5, the organic polymer (A) is only a linear organic polymer (A1), and in the curable composition of Example 6, the organic polymer (A) is branched. Only the organic polymer (A2) of. As shown in Table 2, the cured product obtained from the curable compositions of Examples 4, 7 and 8 has 100% elongation of the dumbbell physical properties as compared with the cured product obtained from the curable composition of Example 5. It was found to be excellent in breaking strength of modulus and shear strength. Further, it was found that the cured product obtained from the curable compositions of Examples 4, 7 and 8 was superior in breaking elongation of the dumbbell physical properties as compared with the cured product obtained from the curable composition of Example 6. .. That is, the cured product obtained from the curable compositions of Examples 4, 7 and 8 has an excellent 100% elongation modulus in dumbbell physical properties as compared with the cured product obtained from the curable compositions of Examples 5 and 6. And it was found that both shear strength and excellent breaking strength in shear strength can be achieved.

According to one embodiment of the present invention, it is possible to provide a novel curable composition having excellent initial fixing property. Therefore, in one embodiment of the present invention, the body / parts of an automobile, the body / parts of a large vehicle such as a truck or a bus, the vehicle / parts of a train, the parts for an aircraft, the parts for a ship, the container, the electric / electronic parts, and the household appliances. It can be suitably used in the field of building materials such as products, various mechanical parts, mirrors, various decorative board panels, and sashes.

Claims

It contains 100 parts by weight of an organic polymer (A) having a hydrolyzable silicon group, 10 parts by weight to 500 parts by weight of a polyvinyl chloride resin (B), and 150 parts by weight to 500 parts by weight of calcium carbonate (C).
A curable composition having a mode diameter of the polyvinyl chloride resin (B) of 0.10 μm to 0.50 μm.
The curable composition according to claim 1, further containing 2 parts by weight to 10 parts by weight of the dehydrating agent (D).
The ratio ((B) / (C)) of the content of the polyvinyl chloride resin (B) to the content of the calcium carbonate (C) is 0.2 to 0.8, according to claim 1 or 2. The curable composition according to description.
The curability according to any one of claims 1 to 3, wherein the organic polymer (A) is a mixture of a linear organic polymer (A1) and a branched organic polymer (A2). Composition.
The curable composition according to any one of claims 1 to 4, wherein the content of the calcium carbonate (C) is 250 parts by weight to 500 parts by weight with respect to 100 parts by weight of the organic polymer (A). thing.
The calcium carbonate (C) includes calcium carbonate (C1) having a volume average particle diameter of 0.05 μm to 0.15 μm and calcium carbonate (C2) having a volume average particle diameter of 0.70 μm to 5.00 μm. Including
The ratio of the weight of the calcium carbonate (C1) to the weight of the calcium carbonate (C2) (weight of the calcium carbonate (C1) / weight of the calcium carbonate (C2)) is 1.0 or less, claim 1. The curable composition according to any one of 5 to 5.
A cured product obtained by curing the curable composition according to any one of claims 1 to 6.
An adhesive containing the curable composition according to any one of claims 1 to 6.