JP5565220B2 - Moisture curable resin composition - Google Patents

Description

  The present invention relates to a moisture curable resin composition containing an organic polymer containing a hydrolyzable silyl group and capable of ensuring good adhesion even to difficult-to-adhere members such as styrene resins.

  In consideration of the manufacturing cost and resin strength, the housing resin of electrical products such as speakers is generally made of acrylonitrile butadiene styrene (ABS) resin, PS (polystyrene) resin, or a polymer containing only styrene. Styrenic resins such as high-impact polystyrene (HIPS), which is made by adding rubber to crystalline, colorless and transparent general purpose polystyrene (GPPS) to give impact resistance, are used.

  Conventionally, solvent-based adhesives have been mainly used when these resins are bonded. As a solvent-based adhesive, for example, a mixture of a polyoxyalkylene polymer (A) having a reactive silicon group and a vinyl polymer (B) having a hydroxyl group, and a hydrolyzable silicon group can be introduced into the hydroxyl portion. A curable composition containing a composition (D) obtained by reacting the compound (C) has been proposed (see, for example, Patent Document 1).

  In recent years, from the viewpoint of reducing the environmental load and improving the working environment and hygiene, there has been a tendency to remove the solvent, and development of a non-solvent adhesive that does not contain an organic solvent has been studied. For example, it contains a main agent (polyol component) and a curing agent (polyisocyanate component), and the polyol component is a polyurethane polyol obtained by reaction of a diol containing a macrodiol, a crosslinkable polyol having three or more hydroxyl groups, and a diisocyanate. The polyisocyanate component contains a diisocyanate-terminated prepolymer obtained by reacting a diisocyanate containing an araliphatic diisocyanate and a diol containing a macrodiol, and is composed of two components from these polyol component and polyisocyanate component. It has been proposed to prepare a curable solventless adhesive (see, for example, Patent Document 2).

JP 2004-143194 A JP 2010-59362 A

  However, the non-solvent adhesive has a problem in that it does not exhibit a sufficient adhesive force to difficult-to-adhere members such as styrene resins such as ABS resin, PS resin, and HIPS. Further, higher adhesion is desired for other adherends.

  An object of this invention is to provide the moisture curable resin composition which has favorable adhesive force with respect to all the to-be-adhered member parts in view of the said problem.

（式（１）中、Ｒ _１ は、炭素原子数が１〜１０のアルキル基又はアルキレン基であり、Ｒ _２ は、炭素原子数が１〜５のアルキル基であり、ｎは１又は２の整数である。）
（２） 前記有機重合体（Ａ）が、ポリオキシアルキレン重合体である上記（１）に記載の湿気硬化型樹脂組成物。
（３） 前記有機重合体（Ａ）とは異なる加水分解性シリル基を有するビニル重合体（Ｃ）を含み、
前記ビニル重合体（Ｃ）の含有量と前記有機重合体（Ａ）の含有量との比が、５対１００以上５０対１００以下である上記（１）又は（２）に記載の湿気硬化型樹脂組成物。
（４） 前記有機重合体（Ａ）は、加水分解性シリル基として、メチルジメトキシシリル基、メチルジエトキシシリル基、トリメトキシシリル基、及びトリエトキシシリル基のうち少なくとも１つを含む上記（１）から（３）の何れかに記載の湿気硬化型樹脂組成物。
（５） 更に、平均粒子径が０．０５μｍ以上０．２０μｍ以下の脂肪酸処理された膠質炭酸カルシウム（Ｄ）を含み、
前記膠質炭酸カルシウム（Ｄ）の含有量が、前記有機重合体（Ａ）１００質量部に対して５質量部以上５０質量部以下である上記（１）から（４）の何れかに記載の湿気硬化型樹脂組成物。 The present invention includes the following (1) to (5).
(1) an organic polymer (A) having a hydrolyzable silyl group;
Including the compound (B) represented by the following formula (1),
The moisture curing, wherein the content of the compound (B) represented by the following formula (1) is 0.5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the organic polymer (A). Mold resin composition.

(In formula (1), R ₁ is an alkyl group having 1 to 10 carbon atoms or an alkylene group, R ₂ is an alkyl group having 1 to 5 carbon atoms, and n is 1 or 2. (It is an integer.)
(2) The moisture curable resin composition according to the above (1), wherein the organic polymer (A) is a polyoxyalkylene polymer.
(3) including a vinyl polymer (C) having a hydrolyzable silyl group different from the organic polymer (A) ,
The moisture curable type according to the above (1) or (2), wherein the ratio of the content of the vinyl polymer (C) and the content of the organic polymer (A) is 5 to 100 or more and 50 to 100 or less. Resin composition.
(4) The organic polymer (A) contains at least one of a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group, and a triethoxysilyl group as the hydrolyzable silyl group (1 The moisture curable resin composition according to any one of (3) to (3).
(5) In addition, fatty acid-treated colloidal calcium carbonate (D) having an average particle size of 0.05 μm or more and 0.20 μm or less,
The moisture according to any one of (1) to (4), wherein the content of the colloidal calcium carbonate (D) is 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the organic polymer (A). A curable resin composition.

  According to this invention, it can have favorable adhesive force with respect to all the to-be-adhered member parts.

  The present invention will be described in detail below. Note that the present invention is not limited to the embodiments. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art or those that are substantially the same.

（式（１）中、Ｒ _１ は、炭素原子数が１〜１０のアルキル基又はアルキレン基であり、Ｒ _２ は、炭素原子数が１〜５のアルキル基であり、ｎは１又は２の整数である。） The moisture curable resin composition of the present invention (hereinafter referred to as “the composition of the present invention”) includes an organic polymer (A) having a hydrolyzable silyl group and a compound represented by the following formula (1) ( The content of the compound (B) represented by the following formula (1) is 0.5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the organic polymer (A).

(In formula (1), R ₁ is an alkyl group having 1 to 10 carbon atoms or an alkylene group, R ₂ is an alkyl group having 1 to 5 carbon atoms, and n is 1 or 2. (It is an integer.)

<Organic polymer having hydrolyzable silyl group (A)>
The organic polymer (A) in the present invention is a polymer having at least one hydrolyzable silyl group in the molecule. The organic polymer (A) is not particularly limited, and examples thereof include a modified silicone polymer. The modified silicone-based polymer has a property that a siloxane bond is formed by a hydroxy group and / or a hydrolyzable group bonded to a silicon atom to form a cured product by crosslinking.

  The hydrolyzable silyl group is not particularly limited as long as it is a silicon atom-containing group or silanol group having a hydrolyzable group directly bonded to a silicon atom. The hydrolyzable silyl group can cause a condensation reaction such as a dehydration reaction by using a condensation catalyst under conditions where moisture, a crosslinking agent and the like are present. The hydrolyzable silyl group is, for example, a silanol group represented by the following formula (2) or a group in which a hydrolyzable group is bonded to silicon.

In the formula, R ¹ and R ² are each independently represented by an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ³ ) ₃ SiO—. And when two or more R ¹ or R ² are present, they may be the same or different. Here, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ^{3 s} may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a is an integer from 0 to 3, and b is an integer from 0 to 2, respectively. Moreover, b in t groups represented by the following formula (3) may be different. t represents an integer of 0 to 19. However, it is assumed that a + t × b ≧ 1 is satisfied.

  The hydrolyzable group represented by Y is not particularly limited as long as it is a conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Of these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. The group is particularly preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  This hydrolyzable group or hydroxy group can be bonded to one silicon atom in the range of 1 to 3, and (a + tb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxy groups are bonded to the reactive silicon group, they may be the same or different.

The number of silicon atoms forming the hydrolyzable silyl group may be at least one in the molecule, and may be two or more. In the case of silicon atoms linked by a siloxane bond or the like, 20 or more It is preferable that there is also. In particular, among hydrolyzable silyl groups, the hydrolyzable silyl group represented by the following general formula (4) is preferable from the viewpoint of easy availability. In the following formula (4), R ² , Y and a have the same meanings as R ² , Y and a described above.

Specific examples of R ¹ and R ² in the general formula (1) include, for example, alkyl groups such as methyl group and ethyl group; alicyclic hydrocarbon groups such as cyclohexyl group; aryl groups such as phenyl group; benzyl group And a triorganosiloxy group represented by (R ³ ) ₃ SiO— in which R ³ is a methyl group or a phenyl group. R ¹ , R ² and R ³ are particularly preferably methyl groups.

  The organic polymer (A) is not particularly limited as long as it is an organic polymer having at least one hydrolyzable silyl group represented by the above general formula (1) at the end or side chain of the main chain. The hydrolyzable silyl groups bonded to the terminal or side chain of the main chain can be used alone or in combination of two or more.

  The main chain of the organic polymer (A) is, for example, a polyoxyalkylene polymer, a polyether polymer, a polyester polymer, an ether / ester block copolymer, an ethylenically unsaturated compound polymer, or a diene compound. A polymer is mentioned.

The polyoxyalkylene polymer is not particularly limited as long as it is a polymer obtained by ring-opening polymerization of alkylene oxide. For example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyisobutylene, polyoxy Although tetramethylene etc. are mentioned, it is not limited to these. Of these, polyoxypropylene is more preferably used. The molecular chain of the oxyalkylene polymer (A) may consist of only one type of repeating unit, or two or more types may be used in combination. Further, for example, it may be in the form of a block copolymer or a random copolymer of ethylene oxide and propylene oxide. The oxyalkylene polymer may be linear or branched, or a mixture thereof. Among these oxyalkylenes, the molecular chain is substantially the following formula (5):
—CH (CH ₃ ) CH ₂ —O— (5)
Is preferably from the viewpoints of easy handling of the resulting curable composition and physical properties of the cured product. In addition, “substantially” herein may contain other monomers, but the repeating unit represented by the general formula (1) is a monomer unit of the polymer (A). It means 50% by weight or more, preferably 80% by weight or more based on the total amount.

  Examples of the polyether polymer include those having repeating units of ethylene oxide, propylene oxide, butylene oxide, and polyphenylene oxide.

  Examples of the polyester polymer include carboxylic acids such as acetic acid, propionic acid, maleic acid, phthalic acid, citric acid, pyruvic acid, and lactic acid, carboxylic acid anhydrides, their intramolecular and / or intermolecular esters, and substitution thereof. The thing which has a body as a repeating unit is illustrated.

  Examples of the ether / ester block copolymer include those having as a repeating unit both the repeating unit used in the above-mentioned polyether polymer and the repeating unit used in the above-mentioned polyester polymer.

  Examples of the ethylenically unsaturated compound polymer and diene compound polymer include homopolymers such as ethylene, propylene, acrylic ester, methacrylic ester, vinyl acetate, acrylonitrile, styrene, isobutylene, butadiene, isoprene, chloroprene, and the like. These 2 or more types of copolymers are mentioned. More specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer. Polymer, polyisoprene, styrene-isoprene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylate ester, polymethacrylate ester Can be mentioned.

  The modified silicone polymer is not particularly limited with respect to its production method. For example, it can be produced by a conventionally known method as described in Japanese Patent Publication No. 61-18569. Examples of commercially available products include MS polymer S-203, MS polymer S-303, MS polymer S-903, MS polymer S-911, silyl polymer SAT200, silyl polymer MA430, and silyl polymer manufactured by Kaneka Corporation. MAX447: Exastar ESS-3620, Exester ESS-3430, Exester ESS-2420, Exester ESS-2410, etc. manufactured by Asahi Glass Co., Ltd. may be mentioned.

  An organic polymer (A) can be used individually or in combination of 2 types or more, respectively.

  The number average molecular weight (Mn) of the organic polymer (A) is not particularly limited, and from the viewpoint of viscosity and workability, the number average molecular weight (in terms of polystyrene by gel permeation chromatography (GPC) method) ( Mn) is preferably 6,000 or more and 60,000 or less, more preferably 8,000 or more and 50,000 or less, and more preferably 10,000 or more and 30 in view of excellent mechanical properties. It is especially preferable that it is 1,000 or less. In such a range, the viscosity of the curable composition becomes appropriate and handling becomes easy. Further, the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is preferably such that the molecular weight distribution of 1.6 or less is narrow (Mw / Mn ratio is small) in terms of polystyrene by GPC method. Is preferably 5 or less, and more preferably 1.4 or less.

<Compound (B) represented by the above formula (1)>
The compound (B) is a compound represented by the above formula (1). R ₁ is an alkyl group having 2 to 10 carbon atoms, R ₂ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 or 2. R ₁ is preferably an alkyl group having 2 to 10 carbon atoms, more preferably an alkyl group having 2 to 6 carbon atoms. When the number of carbon atoms in R ₁ is less than 2, the number of carbon atoms in R ₁ is 1, which is not preferable because the types of alkyl groups are limited. When the number of carbon atoms in R ₁ exceeds 10, the resulting composition becomes a solid, which is not preferable. R ₂ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms. This is because if the number of carbon atoms in R ₂ exceeds 5, the hydrolysis rate becomes slow, so that the effect cannot be obtained.

When the number of carbon atoms of R ₁ and R ₂ is 2 and n is an integer of 2, compound (B) is synthesized by reaction as shown in the following formula (6), and an adhesion-imparting component is added. . Thereby, the adhesive force to ethylene-type resin, such as ABS, PS, and HIPS, is securable.

  Although content of a compound (B) is 0.5 to 15 mass parts with respect to 100 mass parts of organic polymers (A), More preferably, it is 3 to 10 mass parts. When the content of the compound (B) is less than 0.5 parts by mass with respect to 100 parts by mass of the organic polymer (A), adhesiveness is not exhibited, which is not preferable. If the content of the compound (B) exceeds 15 parts by mass with respect to 100 parts by mass of the organic polymer (A), elongation of the cured product is lost, which is not preferable.

<Vinyl polymer (C)>
The composition of the present invention preferably contains a vinyl polymer (C) having a hydrolyzable silyl group. When a polyoxyalkylene polymer is used as the organic polymer (A), the ratio of the content of the vinyl polymer (C) and the content of the organic polymer (A) is 5: 100 or more and 50: 100 or less. It is preferable. When the ratio of the content of the vinyl polymer (C) and the content of the organic polymer (A) is less than 5: 100, the adhesiveness of the resulting composition is lowered, which is not preferable. Further, if the ratio of the content of the vinyl polymer (C) and the content of the organic polymer (A) exceeds 50 to 100 or less, the viscosity of the composition increases and the surface tack deteriorates. It is not preferable.

  As the vinyl polymer (C) having a hydrolyzable silyl group, for example, products obtained by vinyl polymerization of various acrylic acid monomers can be used. By mixing a small amount of a (meth) acrylic monomer having a hydrolyzable silyl group such as methacryloxysilane, hydrolyzable silyl groups are randomly introduced into the vinyl polymer obtained as a product.

<Colloidal calcium carbonate (D)>
The composition of the present invention preferably contains colloidal calcium carbonate (D) whose surface is treated with a fatty acid. In the colloidal calcium carbonate (D) contained in the composition of the present invention, the average particle size is 0.05 μm or more and 0.20 μm or less, preferably 0.06 μm or more and 0.10 μm or less, more preferably It is 0.07 μm or more and 0.09 μm or less. When the average particle diameter of the colloidal calcium carbonate (D) is less than 0.05 μm, the dispersion of the colloidal calcium carbonate (D) is poor and cannot be kneaded well, and it is difficult to increase the viscosity, and the appearance of the composition of the present invention deteriorates. It is not preferable. Moreover, when the average particle diameter of colloidal calcium carbonate (D) exceeds 0.20 μm, the strength after curing of the composition of the present invention is lowered, which is not preferable.

  The content of colloidal calcium carbonate (D) is preferably 5 parts by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the organic polymer (A). Preferably, it is 5 parts by mass or more and 15 parts by mass or less. By making content of colloidal calcium carbonate (D) into the said range, while being able to suppress manufacturing cost, the adhesive force of the composition obtained can be improved. Adhesiveness is inferior that content of colloidal calcium carbonate (D) is less than 5 mass parts. Moreover, when content of colloidal calcium carbonate (D) exceeds 50 mass parts, it is because the viscosity of the composition of this invention becomes high too much and is inferior to workability | operativity.

  The surface treatment method of colloidal calcium carbonate (D) may be a conventionally known method, and is described in detail, for example, in JP-A-2-38309. Examples of fatty acids include linear saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid and melicic acid; unsaturated fatty acids such as celetic acid and sorbic acid And aromatic carboxylic acids such as benzoic acid and phenylacetic acid. Among these, palmitic acid and stearic acid are preferable in terms of thermal stability of the surface treatment and thixotropic properties.

  Examples of a method for surface-treating calcium carbonate with the above fatty acid include a method in which a fatty acid is adsorbed on the surface of calcium carbonate by adding the fatty acid to calcium carbonate and kneading, spraying or dipping.

  The surface treatment amount of the fatty acid is usually 1.0% by mass or more and 10% by mass or less with respect to calcium carbonate. Specifically, EDS-D10A (manufactured by Shiroishi Kogyo Co., Ltd.), Calfine 200 (manufactured by Maruo Calcium Co., Ltd.), Carlex 50 (manufactured by Maruo Calcium Co., Ltd.), Gelton 50 (Shiraishi Co., Ltd.) As a heavy calcium carbonate, Softon 3200 (manufactured by Bihoku Powder Chemical Co., Ltd.) and the like are preferably used. These may be used in combination.

  In the case where the organic polymer (A) is a polyoxyalkylene polymer and contains a vinyl polymer (C), the content of the colloidal calcium carbonate (D) is such that the polyoxyalkylene polymer and the vinyl polymer (C) Is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less, and 5 parts by mass or more and 15 parts by mass or less. Is more preferable. Adhesiveness of the composition of this invention is inferior that content of colloidal calcium carbonate (D) is less than 5 mass parts. Moreover, when content of colloidal calcium carbonate (D) exceeds 50 mass parts, it is because the viscosity of the composition of this invention becomes high too much and is inferior to workability | operativity.

  Thus, the composition of the present invention includes the organic polymer (A) having a hydrolyzable silyl group and the compound (B) represented by the above formula (1), and is represented by the above formula (1). The content of the compound (B) is 0.5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the organic polymer (A). Since the adhesion-imparting component is added to the compound (B), it can have a good adhesion to any adherent member such as an ethylene resin such as ABS, PS, and HIPS.

  The composition of the present invention can contain various additives as necessary in addition to the above-described components within a range not impairing the object of the present invention. Examples of the additive include a filler, a plasticizer, a silane coupling agent, a pigment, a dye, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, an adhesion imparting agent, a stabilizer, and a dispersant. .

  Examples of the filler include organic or inorganic materials having various shapes. For example, wax stone clay, kaolin clay, calcined clay; silica sand, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; calcium carbonate, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide Magnesium carbonate, zinc carbonate; organic or inorganic fillers such as carbon black; and these fatty acids, resin acids, fatty acid ester-treated products, and fatty acid ester urethane compound-treated products.

  Examples of the plasticizer include polypropylene glycol (B), diisononyl phthalate (DINP), dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dipenzoate, pentaerythritol Examples include esters; butyl oleate, methyl acetylricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester; alkyl sulfonic acid phenyl ester (for example, mezamol manufactured by Bayer). In addition, an acrylic polymer that is polymerized at a polymerization temperature of 150 ° C. or more and 350 ° C. or less and having a number average molecular weight of 500 or more and 5000 or less without using a chain transfer agent can be used.

  As the silane coupling agent, for example, trimethoxyvinylsilane and γ-glycidoxypropyltrimethoxysilane are particularly preferable because they are excellent in the effect of improving the adhesion to a wet surface and are general-purpose compounds.

  The pigment may be either an inorganic pigment or an organic pigment. For example, an organic pigment such as titanium dioxide, zinc oxide, ultramarine blue, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate inorganic pigment, azo pigment, copper phthalocyanine pigment, or the like can be used.

  The dye is not particularly limited, and conventionally known dyes can be used. For example, black dye, yellow dye, red dye, blue dye, and brown dye can be mentioned.

  Examples of the antiaging agent include hindered phenol compounds and hindered amine compounds.

  Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

  Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

  Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.

  Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, and xylene resins.

  Examples of the stabilizer include fatty acid silyl esters and fatty acid amide trimethylsilyl compounds.

  The method for producing the composition of the present invention is not particularly limited. For example, each of the above components is stirred in a roll, a kneader, an extruder, a universal agitator, a mixing mixer, etc. under reduced pressure or in an inert gas atmosphere such as nitrogen. Examples of the method include mixing by sufficiently kneading using an apparatus and uniformly dispersing.

  The composition of the present invention is a moisture-curing type, and can be used as a one-component curable composition in which all the blended components are blended and stored in advance and cured by moisture in the air after construction. Further, as a curing agent, components such as a curing catalyst, a filler, a plasticizer, and water are blended in advance and used as a two-component type in which the blending agent (material) and the polymer composition are mixed before use. You can also. When the composition of the present invention is of a one-component type, all the blended components are blended in advance. Therefore, the blended components containing moisture are used after being dehydrated and dried in advance, or are dehydrated by decompression during blending and kneading. Is preferred. When the composition of the present invention is exposed to moisture, the curing reaction proceeds by hydrolysis of the hydrolyzable silyl group. Therefore, the obtained composition of the present invention is stored in a closed container, and a cured product can be obtained at room temperature by using moisture in the air at the time of use. In addition, the curing reaction can be advanced by appropriately supplying water.

  The use of the composition of the present invention is not particularly limited, but the composition of the present invention has the excellent characteristics as described above, so it is for civil engineering, concrete, wood, metal, glass, and plastic. It is suitably used for applications such as sealing materials such as adhesives, sealing agents, potting agents, elastic adhesives, coating materials, lining materials, structural adhesives in concrete and mortar, and cracking injection materials.

  The method for adhering the composition of the present invention to a hardly adhesive member is not particularly limited. For example, the composition of the present invention is applied and immersed in a hardly adhesive member, and the composition of the present invention is used at a thickness of 1 mm or more and 10 mm or less. Can be adhered. The composition of the present invention can be cured by moisture such as moisture, and the curing is preferably performed under conditions of 5 ° C. or more and 40 ° C. or less and 30% RH or more and 70% RH or less.

Hereinafter, the present invention will be specifically described by way of examples. However, the invention according to the present embodiment is not limited to these.
<Examples 1-21 and Comparative Examples 1-4>
[Adjustment of moisture curable resin composition]
Table 1 shows the components used when adjusting the moisture-curable resin composition and the amount (parts by mass) added. The components shown in Table 1 were blended in the addition amount (parts by mass) shown in the same table and mixed uniformly to prepare each composition shown in Table 1. The amount (parts by mass) of each component in each example and comparative example is as shown in Table 1. In addition, Table 2 shows each component used when adjusting the compounds (B) 1 to (B) 6 shown in Table 1 and the amount added (parts by mass) thereof. The components shown in Table 2 were blended in the addition amount (parts by mass) shown in the same table, and these were uniformly mixed to prepare compounds (B) 1 to (B) 6 shown in Table 2. The amount (parts by mass) of each component of compounds (B) 1 to (B) 6 is as shown in Table 2.

[Evaluation]
Using each moisture curable resin composition obtained as described above, the viscosity and adhesiveness of each moisture curable resin composition were evaluated.

(viscosity)
The viscosity of each obtained moisture curable resin composition was measured at 25 ° C. with a rotational speed of 20 rpm using a rotational viscometer (TV20 type viscometer, manufactured by Toki Sangyo Co., Ltd.) and a No. 6 rotor. The test results are shown in Table 1. If the viscosity at 25 ° C. was 150 Pa · s or less, it was judged that the workability was good.

(Adhesiveness)
According to JIS A 5758 5.12, this moisture curable resin composition was applied on a resin substrate so that the film thickness was about 3 mm. Thereafter, the moisture curable resin composition was treated at 23 ° C. and 50% R.D. H. The cured test piece was prepared by allowing it to stand for 5 days in the atmosphere and curing. The cured test piece was subjected to a tensile adhesion test at a speed of 50 mm / min. The fracture form in the tensile adhesion test was confirmed visually. The test results were evaluated as follows, and the test results are shown in Table 1. Three types of resin substrates, ABS, PS, and HIPS, were used. In Table 1, o, Δ, and x represent the following states, respectively. If the cohesive failure (CF) was 50% or more of the entire cured test piece, it was judged that the adhesion was good.
○: CF is 90% or more of the entire cured specimen (interfacial fracture (AF) is less than 90%)
Δ: CF is 50% or more and less than 90% of the entire cured test piece ×: CF is 10% or less of the entire cured test piece

The components shown in Tables 1 to 3 are as follows.
Organic polymer (A): TMS polymer (trade name: SAX-510 (molecular weight: 29000, linear), manufactured by Kaneka Corporation)
-Mixture: Mixture of organic polymer (A) and vinyl polymer (B) (trade name "MA-451 (molecular weight: 29000, linear)", manufactured by Kaneka Corporation)
・ 3-isocyanatepropyltriethoxysilane: trade name “KBE-9007”, manufactured by Shin-Etsu Chemical Co., Ltd. ・ 3-isocyanatepropyltrimethoxysilane: trade name “Y-5187”, manufactured by Momentive Performance Materials, Inc. (D): Colloidal calcium carbonate whose surface is treated with fatty acid (trade name “Neolite SP”, manufactured by Takehara Chemical Co., Ltd.)
・ Epoxysilane: Trade name “A-187”, manufactured by Momentive Performance Materials ・ Vinylsilane: Trade name “A-171”, manufactured by Momentive Performance Materials ・ Diaminosilane: Trade name “A-1120” , Made by Momentive Performance Materials, Inc.-dioctyl tin: trade name "Neostan S1", made by Nitto Kasei

  In addition, 3-isocyanatopropyltriethoxysilane is represented by the following formula (7), and 3-isocyanatepropyltrimethoxysilane is represented by the following formula (8).

  As shown in Table 1, in Examples 1 to 21 and Comparative Examples 1 to 4, the obtained moisture curable resin compositions all had a viscosity of 150 Pa · s or less. Therefore, it was confirmed that the moisture curable resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 have good workability.

  The moisture-curing resin compositions obtained from Comparative Examples 1, 3, and 4 are mostly interface fracture (AF) with respect to the ABS, PS, and HIPS used as the resin substrate. Yes, the proportion of CF in the entire cured test piece was 10% or less. Further, in the moisture curable resin composition obtained from Comparative Example 2, when ABS or HIPS was used as the resin substrate, the failure mode of the cured test piece was almost CF, and the CF in the entire cured test piece was CF. However, when PS is used as the resin substrate, the fracture mode of the cured specimen is mostly AF, and the percentage of CF in the entire cured specimen is 10% or less. It was. On the other hand, the moisture curable resin composition obtained from Examples 1, 2, 5, 8 to 10, 13, 14, 17, 18, and 21 corresponds to any of ABS, PS, and HIPS used as the resin substrate. However, CF was the fracture form of 50% or more of the entire cured test piece. In addition, the moisture curable resin composition obtained from Examples 3, 4, 6, 7, 11, 12, 15, 16, 19, and 20 was used for any of ABS, PS, and HIPS used as a resin substrate. 90% or more of the fracture forms in the entire cured test piece was CF. Therefore, it was confirmed that the moisture curable resin compositions obtained from Examples 1 to 7 have good adhesion to resin substrates such as ABS, PS, and HIPS.

  Therefore, the moisture curable resin composition obtained from Examples 1 to 21 maintains the same viscosity as the conventional one, like the moisture curable resin composition obtained from Comparative Examples 1 to 4. Example 1 The moisture curable resin composition obtained from ˜21 has a cured product adhesiveness to any resin substrate such as an ethylene resin compared to the moisture curable resin composition obtained from Comparative Examples 1 to 4. Since it was excellent, it turned out that the reliability as a moisture hardening type resin composition is high. Therefore, like Examples 1-21, the organic polymer (A) which has a hydrolyzable silyl group, and the compound (B) represented by the said Formula (1) are represented by the said Formula (1). By keeping the content of the compound (B) to be within a predetermined range, the resulting moisture curable resin composition maintains a high viscosity, and the adhesiveness after curing is improved with respect to any resin substrate Therefore, it was found that a highly reliable moisture-curable resin composition can be obtained as an adhesive for difficult-to-adhere members such as ethylene resins.

  As described above, according to the moisture curable resin composition of the present invention, it is possible to provide a cured product having a stable adhesive force even to difficult-to-adhere members such as ethylene resins. The resin composition can be suitably used as an adhesive for any member.

Claims (5)

An organic polymer (A) having a hydrolyzable silyl group;
Including the compound (B) represented by the following formula (1),
The moisture curing, wherein the content of the compound (B) represented by the following formula (1) is 0.5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the organic polymer (A). Mold resin composition.

(In formula (1), R ₁ is an alkyl group having 1 to 10 carbon atoms or an alkylene group, R ₂ is an alkyl group having 1 to 5 carbon atoms, and n is 1 or 2. (It is an integer.)   The moisture curable resin composition according to claim 1, wherein the organic polymer (A) is a polyoxyalkylene polymer. A vinyl polymer (C) having a hydrolyzable silyl group different from the organic polymer (A) ,
The moisture curable resin composition according to claim 1 or 2, wherein a ratio of the content of the vinyl polymer (C) and the content of the organic polymer (A) is 5 to 100 or more and 50 to 100 or less. . The organic polymer (A) contains at least one of a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group, and a triethoxysilyl group as a hydrolyzable silyl group. The moisture curable resin composition according to any one of the above. Furthermore, it contains fatty acid-treated colloidal calcium carbonate (D) having an average particle size of 0.05 μm or more and 0.20 μm or less,
The content of colloidal calcium carbonate (D) is, the organic polymer (A) moisture curing according 50 parts by mass or more 5 parts by mass with respect to 100 parts by mass in a claim 1 or less in any one of the 4 Mold resin composition.